Electrocatalytic oxygen reduction reaction(ORR)is one of the most important reactions in electrochemical energy technologies such as fuel cells and metal–O2/air batteries,etc.However,the essential catalysts to overco...Electrocatalytic oxygen reduction reaction(ORR)is one of the most important reactions in electrochemical energy technologies such as fuel cells and metal–O2/air batteries,etc.However,the essential catalysts to overcome its slow reaction kinetic always undergo a complex dynamic evolution in the actual catalytic process,and the concomitant intermediates and catalytic products also occur continuous conversion and reconstruction.This makes them difficult to be accurately captured,making the identification of ORR active sites and the elucidation of ORR mechanisms difficult.Thus,it is necessary to use extensive in-situ characterization techniques to proceed the real-time monitoring of the catalyst structure and the evolution state of intermediates and products during ORR.This work reviews the major advances in the use of various in-situ techniques to characterize the catalytic processes of various catalysts.Specifically,the catalyst structure evolutions revealed directly by in-situ techniques are systematically summarized,such as phase,valence,electronic transfer,coordination,and spin states varies.In-situ revelation of intermediate adsorption/desorption behavior,and the real-time monitoring of the product nucleation,growth,and reconstruction evolution are equally emphasized in the discussion.Other interference factors,as well as in-situ signal assignment with the aid of theoretical calculations,are also covered.Finally,some major challenges and prospects of in-situ techniques for future catalysts research in the ORR process are proposed.展开更多
The pyrolysis under inert atmosphere has been widely used for the synthesis of metal containing heteroatoms doped carbon materials, versatile catalysts for various reactions. However, it is difficult to prevent metal ...The pyrolysis under inert atmosphere has been widely used for the synthesis of metal containing heteroatoms doped carbon materials, versatile catalysts for various reactions. However, it is difficult to prevent metal nanoparticles aggregation during pyrolysis process. Herein, we reported the efficient synthesis of nitrogen doped carbon hollow nanospheres with cobalt nanoparticles (Co NP, ca. 10nm in size) distributed uniformly in the shell via pyrolysis of yolk-shell structured Zn-Co-ZIFs@polydopamine (PDA). PDA acted as both protection layer and carbon source, which successfully prevented the aggregation of cobalt nanoparticles during high-temperature pyrolysis process. The Co NP and N containing carbon (Co NP/NC) hollow nanospheres were active for both oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), affording overpotential of 430 mV at 10 mA/cm2 for OER in 1 M KOH and comparable half-wave potential to that of Pt/C (0.80V vs RHE) for ORR in 0.1 M KOH. The superior performance of carbon hollow nanospheres for both OER and ORR was mainly attributed to its small metal nanoparticles, N-doping and hollow nanostructure. The protection and confinement effect that originated from PDA coating strategy could be extended to the synthesis of other hollow structured carbon materials, especially the ones with small metal nanoparticles.展开更多
Emerging as a prominent area of focus in energy conversion and storage technologies,the development of highly active metal-based single-atom catalysts(SACs)holds great significance in searching alternatives to replace ...Emerging as a prominent area of focus in energy conversion and storage technologies,the development of highly active metal-based single-atom catalysts(SACs)holds great significance in searching alternatives to replace precious metals toward the efficient,stable,and low-cost hydrogen evolution reaction(HER),as well as the oxygen evolution reaction(OER)and the oxygen reduction reaction(ORR).Combining the tremendous tunability of ligand and coordination environment with rich metal-based electrocatalysts can create breakthrough opportunities for achieving both high stability and activity.Herein,we propose a novel and stable holey graphene-like carbon nitride monolayer g-C_(16)N5(N_(4)@g-C_(16)N_(3))stoichiometries interestingly behaving as a natural substrate for constructing SACs((TM-N_(4))@g-C_(16)N_(3)),whose evenly distributed holes map rich and uniform nitrogen coordination positions with electron-rich lone pairs for anchoring transition metal(TM)atoms.Then,we employed density functional theory(DFT)calculations to systematically investigate the electrocatalytic activity of(TM-N_(4))@g-C_(16)N_(3) toward HER/OER/ORR,meanwhile considering the synergistic modulation of H-loading and O-coordination((TM-N_(x)O_(4-x))@g-C_(16)N_(3)^(-)H_(3),x=0–4).Together a“four-step procedure”screening mechanism with the first-principles high-throughput calculations,we find that(Rh-N_(4))and(Ir-N_(2)O_(2)-II)distributed on g-C_(16)N_(3)^(-)H_(3) can modulate the adsorption strength of the adsorbates,thus achieving the best HER/OER/ORR performance among 216 candidates,and the lowest overpotential of 0.098/0.3/0.46 V and 0.06/0.48/0.45 V,respectively.Additionally,the d-band center,crystal orbital Hamilton population(COHP),and molecular orbitals are used to reveal the OER/ORR activity source.Particularly,the Rh/Ir-d orbital is dramatically hybridized with the O-p orbital of the oxygenated adsorbates,so that the lone-electrons incipiently locate at the antibonding orbital pair up and populate the downward bonding orbital,allowing oxygenated intermediates to be adsorbed onto(TM-N_(x)O_(4-x))@g-C_(16)N_(3)^(-)H_(3) appropriately.展开更多
The long-range periodically ordered atomic structures in intermetallic nanoparticles(INPs)can significantly enhance both the electrocatalytic activity and electrochemical stability toward the oxygen reduction reaction...The long-range periodically ordered atomic structures in intermetallic nanoparticles(INPs)can significantly enhance both the electrocatalytic activity and electrochemical stability toward the oxygen reduction reaction(ORR)compared to the disordered atomic structures in ordinary solid-solution alloy NPs.Accordingly,through a facile and scalable synthetic method,a series of carbon-supported ultrafine Pt_3Co_(x)Mn_(1-x)ternary INPs are prepared in this work,which possess the"skin-like"ultrathin Pt shells,the ordered L1_(2) atomic structure,and the high-even dispersion on supports(L1_(2)-Pt_3Co_(x)Mn_(1-x)/~SPt INPs/C).Electrochemical results present that the composition-optimized L1_(2)-Pt_3Co_(0.7)Mn_(0.3)/~SPt INPs/C exhibits the highest electrocata lytic activity among the series,which are also much better than those of the pristine ultrafine Pt/C.Besides,it also has a greatly enhanced electrochemical stability.In addition,the effects of annealing temperature and time are further investigated.More importantly,such superior ORR electrocatalytic performance of L1_(2)-Pt_3Co_(0.7)Mn_(0.3)/~SPt INPs/C are also well demonstrated in practical fuel cells.Physicochemical characterization analyses further reveal the major origins of the greatly enhanced ORR electrocata lytic performance:the Pt-Co-Mn alloy-induced geometric and ligand effects as well as the extremely high L1_(2) atomic-ordering degree.This work not only successfully develops a highly active and stable ordered ternary intermetallic ORR electrocatalyst,but also elucidates the corresponding"structure-function"relationship,which can be further applied in designing other intermetallic(electro)catalysts.展开更多
Metal-organic frameworks recently have been burgeoning and used as precursors to obtain various metal-nitrogen-carbon catalysts for oxygen reduction reaction(ORR).Although rarely studied,Mn-N-C is a promising catalyst...Metal-organic frameworks recently have been burgeoning and used as precursors to obtain various metal-nitrogen-carbon catalysts for oxygen reduction reaction(ORR).Although rarely studied,Mn-N-C is a promising catalyst for ORR due to its weak Fenton reaction activity and strong graphitization catalysis.Here,we developed a facile strategy for anchoring the atomically dispersed nitrogen-coordinated single Mn sites on carbon nanosheets(MnNCS)from an Mn-hexamine coordination framework.The atomically dispersed Mn-N_(4) sites were dispersed on ultrathin carbon nanosheets with a hierarchically porous structure.The optimized MnNCS displayed an excellent ORR performance in half-cells(0.89 V vs.reversible hydrogen electrode(RHE)in base and 0.76 V vs.RHE in acid in half-wave potential)and Zn-air batteries(233 mW cm^(−2)in peak power density),along with significantly enhanced stability.Density functional theory calculations further corroborated that the Mn-N_(4)-C(12)site has favorable adsorption of*OH as the rate-determining step.These findings demonstrate that the metal-hexamine coordination framework can be used as a model system for the rational design of highly active atomic metal catalysts for energy applications.展开更多
Fe-N-doped carbon materials(Fe-N-C)are promising candidates for oxygen reduction reaction(ORR)relative to Pt-based catalysts in proton exchange membrane fuel cells(PEMFCs).However,the intrinsic contributions of Fe-N_(...Fe-N-doped carbon materials(Fe-N-C)are promising candidates for oxygen reduction reaction(ORR)relative to Pt-based catalysts in proton exchange membrane fuel cells(PEMFCs).However,the intrinsic contributions of Fe-N_(4)moiety with different chemical/spin states(e.g.D1,D2,D3)to ORR are unclear since various states coexist inevitably.In the present work,Fe-N-C core-shell nanocatalyst with single lowspin Fe(Ⅱ)-N_(4)species(D1)is synthesized and identified with ex-situ ultralow temperature Mossbauer spectroscopy(T=1.6 K)that could essentially differentiate various Fe-N_(4)states and invisible Fe-O species.By quantifying with CO-pulse chemisorption,site density and turnover frequency of Fe-N-C catalysts reach 2.4×10^(-9)site g^(-1)and 23 e site~(-1)s^(-1)during the ORR,respectively.Half-wave potential(0.915V_(RHE))of the Fe-N-C catalyst is more positive(approximately 54 mV)than that of Pt/C.Moreover,we observe that the performance of PEMFCs on Fe-N-C almost achieves the 2025 target of the US Department of Energy by demonstrating a current density of 1.037 A cm^(-2)combined with the peak power density of 0,685 W cm^(-2),suggesting the critical role of Fe(Ⅱ)-N_(4)site(D1).After 500 h of running,PEMFCs still deliver a power density of 1.26 W cm^(-2)at 1.0 bar H_(2)-O_(2),An unexpected rate-determining step is figured out by isotopic labelling experiment and theoretical calculation.This work not only offers valuable insights regarding the intrinsic contribution of Fe-N_(4)with a single spin state to alkaline/acidic ORR,but also provides great opportunities for developing high-performance stable PEMFCs.展开更多
Despite substantial efforts in developing high-performance catalysts for the oxygen reduction reaction(ORR),the persistent challenge lies in the high onset overpotential of the ORR,and the effect of the elec-trolyte s...Despite substantial efforts in developing high-performance catalysts for the oxygen reduction reaction(ORR),the persistent challenge lies in the high onset overpotential of the ORR,and the effect of the elec-trolyte solution cannot be ignored.Consequently,we have systematically investigated the impact of adsorbate species and concentration,as well as solution pH,on the ORR activity on Pt(111)and Pt(poly)electrodes.The results all tend to establish a linear quantitative relationship between the onset potential for ORR and the adsorption equilibrium potential of the adsorbate.This finding indicates the decisive role of adsorbates in the onset potential for ORR,suggesting that the adsorption potential of adsorbates can serve as an intuitive criterion for ORR activity.Additional support for this conclusion is derived from experimental results obtained from the oxygen evolution reaction on Pt(poly)with different adsorbate species and from the hydrogen evolution reaction on Pt(111)with iodine adsorption.We further propose both an empirical equation for the onset potential for ORR and the concept of a potential-regulated adsor-bate shielding effect to elucidate the influence of adsorbates on ORR activity.This study provides new insights into the high onset overpotential of the ORR and offers potential strategies for predicting and enhancingORRactivity inthefuture.展开更多
Dual-atom catalysts(DACs) afford promising potential for oxygen reduction electrocatalysis due to their high atomic efficiency and high intrinsic activity.However,precise construction of dual-atom sites remains a chal...Dual-atom catalysts(DACs) afford promising potential for oxygen reduction electrocatalysis due to their high atomic efficiency and high intrinsic activity.However,precise construction of dual-atom sites remains a challenge.In this work,a post-modification strategy is proposed to precisely fabricate DACs for oxygen reduction electrocatalysis.Concretely,a secondary metal precursor is introduced to the primary single-atom sites to introduce direct metal-metal interaction,which ensures the formation of desired atom pair structure during the subsequent pyrolysis process and allows for successful construction of DACs.The as-prepared FeCo-NC DAC exhibits superior oxygen reduction electrocatalytic activity with a half-wave potential of 0,91 V vs.reversible hydrogen electrode.Zn-air batteries equipped with the FeCo-NC DAC demonstrate higher peak power density than those with the Pt/C benchmark.More importantly,this post-modification strategy is demonstrated universal to achieve a variety of dual-atom sites.This work presents an effective synthesis methodology for precise construction of catalytic materials and propels their applications in energy-related devices.展开更多
Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utiliz...Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utilization and exceptional catalytic functionality.Furthermore,accurately controlling atomic physical properties including spin,charge,orbital,and lattice degrees of atomically dispersed catalysts can realize the optimized chemical properties including maximum atom utilization efficiency,homogenous active centers,and satisfactory catalytic performance,but remains elusive.Here,through physical and chemical insight,we review and systematically summarize the strategies to optimize atomically dispersed ORR catalysts including adjusting the atomic coordination environment,adjacent electronic orbital and site density,and the choice of dual-atom sites.Then the emphasis is on the fundamental understanding of the correlation between the physical property and the catalytic behavior for atomically dispersed catalysts.Finally,an overview of the existing challenges and prospects to illustrate the current obstacles and potential opportunities for the advancement of atomically dispersed catalysts in the realm of electrocatalytic reactions is offered.展开更多
The high-temperature pyrolysis process for preparing M–N–C single-atom catalyst usually results in high heterogeneity in product structure concurrently contains multiscale metal phases from single atoms(SAs),atomic ...The high-temperature pyrolysis process for preparing M–N–C single-atom catalyst usually results in high heterogeneity in product structure concurrently contains multiscale metal phases from single atoms(SAs),atomic clusters to nanoparticles.Therefore,understanding the interactions among these components,especially the synergistic effects between single atomic sites and cluster sites,is crucial for improving the oxygen reduction reaction(ORR)activity of M–N–C catalysts.Accordingly,herein,we constructed a model catalyst composed of both atomically dispersed FeN4 SA sites and adjacent Fe clusters through a site occupation strategy.We found that the Fe clusters can optimize the adsorption strength of oxygen reduction intermediates on FeN4 SA sites by introducing electron-withdrawing–OH ligands and decreasing the d-band center of the Fe center.The as-developed catalyst exhibits encouraging ORR activity with halfwave potentials(E1/2)of 0.831 and 0.905 V in acidic and alkaline media,respectively.Moreover,the catalyst also represents excellent durability exceeding that of Fe–N–C SA catalyst.The practical application of Fe(Cd)–CNx catalyst is further validated by its superior activity and stability in a metalair battery device.Our work exhibits the great potential of synergistic effects between multiphase metal species for improvements of singleatom site catalysts.展开更多
Metal-free defective carbon materials with abundant active sites have been widely studied as low-cost and efficient oxygen reduction reaction(ORR)electrocatalysts in metal-air batteries.However,the active sites in def...Metal-free defective carbon materials with abundant active sites have been widely studied as low-cost and efficient oxygen reduction reaction(ORR)electrocatalysts in metal-air batteries.However,the active sites in defective carbon are easily subjected to serious oxidation or hydroxylation during ORR or storage,leading to rapid degradation of activity.Herein,we design a van der Waals heterostructure comprised of vitamin C(VC)and defective carbon(DC)to not only boost the activity but also enhance the durability and storage stability of the DC-VC electrocatalyst.The formation of VC van der Waals between DC and VC is demonstrated to be an effective strategy to protect the defect active sites from oxidation and hydroxylation degradation,thus significantly enhancing the electrochemical durability and storage anti-aging performance.Moreover,the DC-VC van der Waals can reduce the reaction energy barrier to facilitate the ORR.These findings are also confirmed by operando Fourier transform infrared spectroscopy and density functional theory calculations.It is necessary to mention that the preparation of this DC-VC electrocatalyst can be scaled up,and the ORR performance of the largely produced electrocatalyst is demonstrated to be very consistent.Furthermore,the DC-VC-based aluminum-air batteries display very competitive power density with good performance maintenance.展开更多
Developing cost-effective,robust and stable non-precious metal catalysts for oxygen reduction reaction(ORR) is of paramount importance for electrochemical energy conversion devices such as fuel cells and metal-air bat...Developing cost-effective,robust and stable non-precious metal catalysts for oxygen reduction reaction(ORR) is of paramount importance for electrochemical energy conversion devices such as fuel cells and metal-air batteries.Although Fe-N-C single atom catalysts(SACs) have been hailed as the most promising candidate due to the optimal binding strength of ORR intermediates on the Fe-N_(4) sites,they suffer from serious mass transport limitations as microporous templates/substrates,i.e.,zeolitic imidazolate frameworks(ZIFs),are usually employed to host the active sites.Motivated by this challenge,we herein develop a hydrogen-bonded organic framework(HOF)-assisted pyrolysis strategy to construct hierarchical micro/mesoporous carbon nanoplates for the deposition of atomically dispersed Fe-N_(4) sites.Such a design is accomplished by employing HOF nanoplates assembled from 2-aminoterephthalic acid(NH_(2)-BDC) and p-phenylenediamine(PDA) as both soft templates and C,N precursors.Benefitting from the structural merits inherited from HOF templates,the optimized catalyst(denoted as Fe-N-C SAC-950) displays outstanding ORR activity with a high half-wave potential of 0.895 V(vs.reversible hydrogen electrode(RHE)) and a small overpotential of 356 mV at 10 mA cm^(-2) for the oxygen evolution reaction(OER).More excitingly,its application potential is further verified by delivering superb rechargeability and cycling stability with a nearly unfading charge-discharge gap of 0.72 V after 160 h.Molecular dynamics(MD) simulations reveal that micro/mesoporous structure is conducive to the rapid mass transfer of O_(2),thus enhancing the ORR performance.In situ Raman results further indicate that the conversion of O_(2) to~*O_(2)-the rate-determining step(RDS) for Fe-N-C SAC-950.This work will provide a versatile strategy to construct single atom catalysts with desirable catalytic properties.展开更多
Transition metal-nitrogen-carbon(M-N-C)as a promising substitute for the conventional noble metalbased catalyst still suffers from low activity and durability for oxygen reduction reaction(ORR)in proton exchange membr...Transition metal-nitrogen-carbon(M-N-C)as a promising substitute for the conventional noble metalbased catalyst still suffers from low activity and durability for oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs).To tackle the issue,herein,a new type of sulfur-doped ironnitrogen-hard carbon(S-Fe-N-HC)nanosheets with high activity and durability in acid media were developed by using a newly synthesized precursor of amide-based polymer with Fe ions based on copolymerizing two monomers of 2,5-thiophene dicarboxylic acid(TDA)as S source and 1,8-diaminonaphthalene(DAN)as N source via an amination reaction.The as-synthesized S-Fe-N-HC features highly dispersed atomic Fe Nxmoieties embedded into rich thiophene-S doped hard carbon nanosheets filled with highly twisted graphite-like microcrystals,which is distinguished from the majority of M-N-C with soft or graphitic carbon structures.These unique characteristics endow S-Fe-N-HC with high ORR activity and outstanding durability in 0.5 M H_(2)SO_(4).Its initial half-wave potential is 0.80 V and the corresponding loss is only 21 m V after 30,000 cycles.Meanwhile,its practical PEMFC performance is a maximum power output of 628.0 mW cm^(-2)and a slight power density loss is 83.0 m W cm^(-2)after 200-cycle practical operation.Additionally,theoretical calculation shows that the activity of Fe Nxmoieties on ORR can be further enhanced by sulfur doping at meta-site near FeN_(4)C.These results evidently demonstrate that the dual effect of hard carbon substrate and S doping derived from the precursor platform of amid-polymers can effectively enhance the activity and durability of Fe-N-C catalysts,providing a new guidance for developing advanced M-N-C catalysts for ORR.展开更多
Metal-organic frameworks and covalent organic frameworks have been widely employed in electrochemical catalysis owing to their designable skeletons,controllable porosities,and well-defined catalytic centers.However,th...Metal-organic frameworks and covalent organic frameworks have been widely employed in electrochemical catalysis owing to their designable skeletons,controllable porosities,and well-defined catalytic centers.However,the poor chemical stability and low electron conductivity limited their activity,and single-functional sites in these frameworks hindered them to show multifunctional roles in catalytic systems.Herein,we have constructed novel metal organic polymers(Co-HAT-CN and Ni-HAT-CN)with dual catalytic centers(metal-N_(4) and metal-N_(2))to catalyze oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).By using different metal centers,the catalytic activity and selectivity were well-tuned.Among them,Co-HAT-CN catalyzed the ORR in a 4e^(-)pathway,with a half-wave potential of 0.8 V versus RHE,while the Ni-HAT-CN catalyze ORR in a 2e^(-)pathway with H_(2)O_(2) selectivity over 90%.Moreover,the Co-HAT-CN delivered an overpotential of 350 mV at 10 mA cm^(-2) with a corresponding Tafel slope of 24 mV dec^(-1) for OER in a 1.0 M KOH aqueous solution.The experimental results revealed that the activities toward ORR were due to the M-N_(4) sites in the frameworks,and both M-N_(4) and M-N_(2) sites contributed to the OER.This work gives us a new platform to construct bifunctional catalysts.展开更多
metal oxide electronic interactions in composite electrocatalysts have a considerable impact on their catalytic capability.In this study,we successfully synthesized an electrocatalytic material composed of MoO_(3)/C s...metal oxide electronic interactions in composite electrocatalysts have a considerable impact on their catalytic capability.In this study,we successfully synthesized an electrocatalytic material composed of MoO_(3)/C speciessupported Pd nanoparticles(Pd-MoO_(3)/C)using a convenient hydrothermal method,which exhibited excellent catalytic activities for both ethanol oxidation and oxygen reduction in KOH media.The specific activity of PdMoO_(3)/C toward ethanol oxidation with MoO_(3)loading(40wt%)was~2.6 times greater than that for the commercial Pd/C(10 wt%)with the same Pd content.In particular,the activity could effectively hold up to~60%of its maximum activity after 500-cycle tests,demonstrating improved cyclical stability.Notably,the fast electron transfer kinetics toward oxygen reduction for Pd-MoO_(3)/C(40%)were also comparable to those of commercial Pt/C(20 wt%)catalysts.These superior electrochemical features are primarily derived from the stronger electronic coupling between Pd and MoO_(3)through charge transfer,which can supply more active centers and improve the anti-poisoning ability.Meanwhile,the MoO_(3)species in the Pd-MoO_(3)/C composite may provide additional benefits in terms of electrical conductivity and dispersion.展开更多
The development of thermodynamically controllable synthetic strategy to manipulate the morphology of ZIF-8 without capping agent is essential to help understanding their facet effect and the structure-activity relatio...The development of thermodynamically controllable synthetic strategy to manipulate the morphology of ZIF-8 without capping agent is essential to help understanding their facet effect and the structure-activity relationship of single atom catalysts derived from ZIF-8.Here,we prepared ZIF-8 with different morphologies(cube,truncated rhombododecahedral and rhombododecahedral)and thus area ratio of exposed{100},{110}facets by a thermodynamically controllable synthetic strategy.When the reaction proceeds under room temperature(30℃),the assembling of ZIF-8 followed an area-reducing layered growth mode,while switched to an integral layered growth mode at lower temperature-40℃.Moreover,this strategy also works to obtain ZIF-8 encapsulated with metal precursors(Fe(acac)_(3),Cu(acac)_(2)and Co(acac)_(2)).Single Fe atom anchored on nitrogen doped carbon catalysts(SA-Fe/CN)derived from Fe-ZIF-8 retain their original morphologies and the unsaturated surface-active sites on{100}facet,which further displays different catalytic performance towards oxygen reduction reaction(ORR).This work not only reveals the different growth pattern of ZIF-8,but also points out a new direction for designing and synthesizing MOFs with different morphology rationally.展开更多
Electrocatalytic oxygen reduction via a two-electron pathway(2e^(-)-ORR)is a promising and eco-friendly route for producing hydrogen peroxide(H_(2)O_(2)).Single-atom catalysts(SACs)typically show excellent selectivity...Electrocatalytic oxygen reduction via a two-electron pathway(2e^(-)-ORR)is a promising and eco-friendly route for producing hydrogen peroxide(H_(2)O_(2)).Single-atom catalysts(SACs)typically show excellent selectivity towards 2e^(-)-ORR due to their unique electronic structures and geometrical configurations.The very low density of single-atom active centers,however,often leads to unsatisfactory H_(2)O_(2)yield rate,significantly inhibiting their practical feasibility.Addressing this,we herein introduce fluorine as a secondary doping element into conventional SACs,which does not directly coordinate with the singleatom metal centers but synergize with them in a remote manner.This strategy effectively activates the surrounding carbon atoms and converts them into highly active sites for 2e^(-)-ORR.Consequently,a record-high H_(2)O_(2)yield rate up to 27 mol g^(-1)h^(-1)has been achieved on the Mo–F–C catalyst,with high Faradaic efficiency of 90%.Density functional theory calculations further confirm the very kinetically facile 2e^(-)-ORR over these additional active sites and the superiority of Mo as the single-atom center to others.This strategy thus not only provides a high-performance electrocatalyst for 2e^(-)-ORR but also should shed light on new strategies to significantly increase the active centers number of SACs.展开更多
Dealloying by which the transition metal is partially or completely leached from an alloy precursor is an effective way to optimize the fundamental effects for further enhancing the electrocatalysis of a catalyst.Here...Dealloying by which the transition metal is partially or completely leached from an alloy precursor is an effective way to optimize the fundamental effects for further enhancing the electrocatalysis of a catalyst.Herein,to address the deficiencies associated with the commonly used dealloying methods,for example,electrochemical and sulfuric acid/nitric acid treatment,we report an acetic acid-assisted mild strategy to dealloy Cu atoms from the outer surface layers of CuPd alloy nanoparticles to achieve high-efficiency electrocatalysis for oxygen reduction and ethanol oxidation in an alkaline electrolyte.The leaching of Cu atoms by acetic acid exerts an additional compressive strain effect on the surface layers and exposes more active Pd atoms,which is beneficial for boosting the catalytic performance of a dealloyed catalyst for the oxygen reduction reaction(ORR)and the ethanol oxidation reaction(EOR).In particular,for ORR,the CuPd nanoparticles with a Pd/Cu molar ratio of 2:1 after acetic dealloying show a half-wave potential of 0.912 V(vs.RHE)and a mass activity of 0.213 AmgPd^(-1) at 0.9 V,respectively,while for EOR,the same dealloyed sample has a mass activity and a specific activity of 8.4 Amg^(-1) and 8.23 mA cm^(-2),respectively,much better than their dealloyed counterparts at other temperatures and commercial Pd/C as well as a Pt/C catalyst.展开更多
Metal-free carbon-based materials are considered as promising oxygen reduction reaction(ORR)electrocatalysts for clean energy conversion,and their highly dense and exposed carbon active sites are crucial for efficient...Metal-free carbon-based materials are considered as promising oxygen reduction reaction(ORR)electrocatalysts for clean energy conversion,and their highly dense and exposed carbon active sites are crucial for efficient ORR.In this work,two unique quasi-three-dimensional cyclotriphosphazene-based covalent organic frameworks(Q3CTP-COFs)and their nanosheets were successfully synthesized and applied as ORR electrocatalysts.The abundant electrophilic structure in Q3CTP-COFs induces a high density of carbon active sites,and the unique bilayer stacking of[6+3]imine-linked backbone facilitates the exposure of active carbon sites and accelerates mass diffusion during ORR.In particular,bulk Q3CTP-COFs can be easily exfoliated into thin COF nanosheets(NSs)due to the weak interlayerπ-πinteractions.Q3CTP-COF NSs exhibit highly efficient ORR catalytic activity(half-wave potential of 0.72 V vs.RHE in alkaline electrolyte),which is one of the best COF-based ORR electrocatalysts reported so far.Furthermore,Q3CTP-COF NSs can serve as a promising cathode for Zn-air batteries(delivered power density of 156 mW cm-2 at 300 mA cm^(-2)).This judicious design and accurate synthesis of such COFs with highly dense and exposed active sites and their nanosheets will promote the development of metal-free carbon-based electrocatalysts.展开更多
Rational design of hierarchically structured electrocatalysts is particularly important for electrocatalytic oxygen reduction reaction(ORR).Here,ZIF-67 crystals are stringed on core-shell Ag@C nanocables using a coord...Rational design of hierarchically structured electrocatalysts is particularly important for electrocatalytic oxygen reduction reaction(ORR).Here,ZIF-67 crystals are stringed on core-shell Ag@C nanocables using a coordinationmodulated process.Upon pyrolysis,Ag@C strings of Co nanoparticles embedded with three-dimensional porous carbon with beads-on-string hierarchical structures are developed.Due to the advantages of the rich electrochemical active sites of Co-based“beads”and the efficient electron transfer pathways via Ag@C“strings,”the resultant NH_(3)-Ag@C@Co-N-C-700 catalyst shows an improved electrocatalytic activity toward ORR.NH_(3)-Ag@C@Co-N-C-700 shows a high onset potential of 0.99 V versus RHE,a high half-wave potential of 0.88 V versus RHE,and a large limiting current of 5.8 mA cm^(-2),which are better than those of commercial Pt/C electrocatalysts.Additionally,the NH_(3)-Ag@C@Co-N-C-700 catalyst shows high stability and preeminent methanol tolerance,which makes NH_(3)-Ag@C@Co-N-C-700 a promising catalyst for oxygen electrocatalysis in fuel cell applications.展开更多
基金the National Natural Science Foundation of China(No.52072256)Shanxi Science and Technology Major Project(No.20201101016)+1 种基金Key R&D program of Shanxi Province(No.202102030201006)Research Project Supported by Shanxi Scholarship Council of China(HGKY2019031).
文摘Electrocatalytic oxygen reduction reaction(ORR)is one of the most important reactions in electrochemical energy technologies such as fuel cells and metal–O2/air batteries,etc.However,the essential catalysts to overcome its slow reaction kinetic always undergo a complex dynamic evolution in the actual catalytic process,and the concomitant intermediates and catalytic products also occur continuous conversion and reconstruction.This makes them difficult to be accurately captured,making the identification of ORR active sites and the elucidation of ORR mechanisms difficult.Thus,it is necessary to use extensive in-situ characterization techniques to proceed the real-time monitoring of the catalyst structure and the evolution state of intermediates and products during ORR.This work reviews the major advances in the use of various in-situ techniques to characterize the catalytic processes of various catalysts.Specifically,the catalyst structure evolutions revealed directly by in-situ techniques are systematically summarized,such as phase,valence,electronic transfer,coordination,and spin states varies.In-situ revelation of intermediate adsorption/desorption behavior,and the real-time monitoring of the product nucleation,growth,and reconstruction evolution are equally emphasized in the discussion.Other interference factors,as well as in-situ signal assignment with the aid of theoretical calculations,are also covered.Finally,some major challenges and prospects of in-situ techniques for future catalysts research in the ORR process are proposed.
文摘The pyrolysis under inert atmosphere has been widely used for the synthesis of metal containing heteroatoms doped carbon materials, versatile catalysts for various reactions. However, it is difficult to prevent metal nanoparticles aggregation during pyrolysis process. Herein, we reported the efficient synthesis of nitrogen doped carbon hollow nanospheres with cobalt nanoparticles (Co NP, ca. 10nm in size) distributed uniformly in the shell via pyrolysis of yolk-shell structured Zn-Co-ZIFs@polydopamine (PDA). PDA acted as both protection layer and carbon source, which successfully prevented the aggregation of cobalt nanoparticles during high-temperature pyrolysis process. The Co NP and N containing carbon (Co NP/NC) hollow nanospheres were active for both oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), affording overpotential of 430 mV at 10 mA/cm2 for OER in 1 M KOH and comparable half-wave potential to that of Pt/C (0.80V vs RHE) for ORR in 0.1 M KOH. The superior performance of carbon hollow nanospheres for both OER and ORR was mainly attributed to its small metal nanoparticles, N-doping and hollow nanostructure. The protection and confinement effect that originated from PDA coating strategy could be extended to the synthesis of other hollow structured carbon materials, especially the ones with small metal nanoparticles.
基金supported by the National Natural Science Foundation of China(No.21905175).
文摘Emerging as a prominent area of focus in energy conversion and storage technologies,the development of highly active metal-based single-atom catalysts(SACs)holds great significance in searching alternatives to replace precious metals toward the efficient,stable,and low-cost hydrogen evolution reaction(HER),as well as the oxygen evolution reaction(OER)and the oxygen reduction reaction(ORR).Combining the tremendous tunability of ligand and coordination environment with rich metal-based electrocatalysts can create breakthrough opportunities for achieving both high stability and activity.Herein,we propose a novel and stable holey graphene-like carbon nitride monolayer g-C_(16)N5(N_(4)@g-C_(16)N_(3))stoichiometries interestingly behaving as a natural substrate for constructing SACs((TM-N_(4))@g-C_(16)N_(3)),whose evenly distributed holes map rich and uniform nitrogen coordination positions with electron-rich lone pairs for anchoring transition metal(TM)atoms.Then,we employed density functional theory(DFT)calculations to systematically investigate the electrocatalytic activity of(TM-N_(4))@g-C_(16)N_(3) toward HER/OER/ORR,meanwhile considering the synergistic modulation of H-loading and O-coordination((TM-N_(x)O_(4-x))@g-C_(16)N_(3)^(-)H_(3),x=0–4).Together a“four-step procedure”screening mechanism with the first-principles high-throughput calculations,we find that(Rh-N_(4))and(Ir-N_(2)O_(2)-II)distributed on g-C_(16)N_(3)^(-)H_(3) can modulate the adsorption strength of the adsorbates,thus achieving the best HER/OER/ORR performance among 216 candidates,and the lowest overpotential of 0.098/0.3/0.46 V and 0.06/0.48/0.45 V,respectively.Additionally,the d-band center,crystal orbital Hamilton population(COHP),and molecular orbitals are used to reveal the OER/ORR activity source.Particularly,the Rh/Ir-d orbital is dramatically hybridized with the O-p orbital of the oxygenated adsorbates,so that the lone-electrons incipiently locate at the antibonding orbital pair up and populate the downward bonding orbital,allowing oxygenated intermediates to be adsorbed onto(TM-N_(x)O_(4-x))@g-C_(16)N_(3)^(-)H_(3) appropriately.
基金supported by the National Key Research and Development Program of China(2021YFB4001301)the Science and Technology Commission of Shanghai Municipality(21DZ1208600)the Oceanic Interdisciplinary Program of Shanghai Jiao Tong University(SL2021ZD105)。
文摘The long-range periodically ordered atomic structures in intermetallic nanoparticles(INPs)can significantly enhance both the electrocatalytic activity and electrochemical stability toward the oxygen reduction reaction(ORR)compared to the disordered atomic structures in ordinary solid-solution alloy NPs.Accordingly,through a facile and scalable synthetic method,a series of carbon-supported ultrafine Pt_3Co_(x)Mn_(1-x)ternary INPs are prepared in this work,which possess the"skin-like"ultrathin Pt shells,the ordered L1_(2) atomic structure,and the high-even dispersion on supports(L1_(2)-Pt_3Co_(x)Mn_(1-x)/~SPt INPs/C).Electrochemical results present that the composition-optimized L1_(2)-Pt_3Co_(0.7)Mn_(0.3)/~SPt INPs/C exhibits the highest electrocata lytic activity among the series,which are also much better than those of the pristine ultrafine Pt/C.Besides,it also has a greatly enhanced electrochemical stability.In addition,the effects of annealing temperature and time are further investigated.More importantly,such superior ORR electrocatalytic performance of L1_(2)-Pt_3Co_(0.7)Mn_(0.3)/~SPt INPs/C are also well demonstrated in practical fuel cells.Physicochemical characterization analyses further reveal the major origins of the greatly enhanced ORR electrocata lytic performance:the Pt-Co-Mn alloy-induced geometric and ligand effects as well as the extremely high L1_(2) atomic-ordering degree.This work not only successfully develops a highly active and stable ordered ternary intermetallic ORR electrocatalyst,but also elucidates the corresponding"structure-function"relationship,which can be further applied in designing other intermetallic(electro)catalysts.
基金Basic and Applied Basic Research Foundation of Guangdong Province,Grant/Award Numbers:2021A1515110245,2022A1515140108,2023B1515040013National Youth Top-notch Talent Support Program,Grant/Award Number:x2qsA4210090+5 种基金Guangzhou Key Research and Development Program,Grant/Award Number:SL2022B03J01256Guangdong Provincial Key Laboratory of Distributed Energy Systems,Grant/Award Number:2020B1212060075Engineering Research Center of None-food Biomass Efficient Pyrolysis and Utilization Technology of Guangdong Higher Education Institutes,Grant/Award Number:2016GCZX009State Key Laboratory of Pulp and Paper Engineering,Grant/Award Numbers:202215,2022PY02Key projects of social science and technology development in Dongguan,Grant/Award Number:20231800936352National Natural Science Foundation of China,Grant/Award Numbers:21736003,21905044,31971614,32071714。
文摘Metal-organic frameworks recently have been burgeoning and used as precursors to obtain various metal-nitrogen-carbon catalysts for oxygen reduction reaction(ORR).Although rarely studied,Mn-N-C is a promising catalyst for ORR due to its weak Fenton reaction activity and strong graphitization catalysis.Here,we developed a facile strategy for anchoring the atomically dispersed nitrogen-coordinated single Mn sites on carbon nanosheets(MnNCS)from an Mn-hexamine coordination framework.The atomically dispersed Mn-N_(4) sites were dispersed on ultrathin carbon nanosheets with a hierarchically porous structure.The optimized MnNCS displayed an excellent ORR performance in half-cells(0.89 V vs.reversible hydrogen electrode(RHE)in base and 0.76 V vs.RHE in acid in half-wave potential)and Zn-air batteries(233 mW cm^(−2)in peak power density),along with significantly enhanced stability.Density functional theory calculations further corroborated that the Mn-N_(4)-C(12)site has favorable adsorption of*OH as the rate-determining step.These findings demonstrate that the metal-hexamine coordination framework can be used as a model system for the rational design of highly active atomic metal catalysts for energy applications.
基金financial support from the“Hundred Talents Program”of the Chinese Academy of Sciencesthe“Young Talents Training Program”of the Shanghai Branch of the Chinese Academy of Sciences+3 种基金the financial support from the Xiamen City Natural Science Foundation of China(3502Z20227085,3502Z20227256)the National Science Youth Foundation of China(22202205)the Fujian Provincial Natural Science Foundation of China(2022J01502)Open Source Foundation of State Key Laboratory of Structural Chemistry。
文摘Fe-N-doped carbon materials(Fe-N-C)are promising candidates for oxygen reduction reaction(ORR)relative to Pt-based catalysts in proton exchange membrane fuel cells(PEMFCs).However,the intrinsic contributions of Fe-N_(4)moiety with different chemical/spin states(e.g.D1,D2,D3)to ORR are unclear since various states coexist inevitably.In the present work,Fe-N-C core-shell nanocatalyst with single lowspin Fe(Ⅱ)-N_(4)species(D1)is synthesized and identified with ex-situ ultralow temperature Mossbauer spectroscopy(T=1.6 K)that could essentially differentiate various Fe-N_(4)states and invisible Fe-O species.By quantifying with CO-pulse chemisorption,site density and turnover frequency of Fe-N-C catalysts reach 2.4×10^(-9)site g^(-1)and 23 e site~(-1)s^(-1)during the ORR,respectively.Half-wave potential(0.915V_(RHE))of the Fe-N-C catalyst is more positive(approximately 54 mV)than that of Pt/C.Moreover,we observe that the performance of PEMFCs on Fe-N-C almost achieves the 2025 target of the US Department of Energy by demonstrating a current density of 1.037 A cm^(-2)combined with the peak power density of 0,685 W cm^(-2),suggesting the critical role of Fe(Ⅱ)-N_(4)site(D1).After 500 h of running,PEMFCs still deliver a power density of 1.26 W cm^(-2)at 1.0 bar H_(2)-O_(2),An unexpected rate-determining step is figured out by isotopic labelling experiment and theoretical calculation.This work not only offers valuable insights regarding the intrinsic contribution of Fe-N_(4)with a single spin state to alkaline/acidic ORR,but also provides great opportunities for developing high-performance stable PEMFCs.
基金supported by the National Natural Science Foundation of China(no.22372154,21972131).
文摘Despite substantial efforts in developing high-performance catalysts for the oxygen reduction reaction(ORR),the persistent challenge lies in the high onset overpotential of the ORR,and the effect of the elec-trolyte solution cannot be ignored.Consequently,we have systematically investigated the impact of adsorbate species and concentration,as well as solution pH,on the ORR activity on Pt(111)and Pt(poly)electrodes.The results all tend to establish a linear quantitative relationship between the onset potential for ORR and the adsorption equilibrium potential of the adsorbate.This finding indicates the decisive role of adsorbates in the onset potential for ORR,suggesting that the adsorption potential of adsorbates can serve as an intuitive criterion for ORR activity.Additional support for this conclusion is derived from experimental results obtained from the oxygen evolution reaction on Pt(poly)with different adsorbate species and from the hydrogen evolution reaction on Pt(111)with iodine adsorption.We further propose both an empirical equation for the onset potential for ORR and the concept of a potential-regulated adsor-bate shielding effect to elucidate the influence of adsorbates on ORR activity.This study provides new insights into the high onset overpotential of the ORR and offers potential strategies for predicting and enhancingORRactivity inthefuture.
基金This work was supported by the National Natural Science Foundation of China(22279008 and 22109082)the Beijing Institute of Technology Research Fund Program for Young Scholarsthe Tsinghua University Initiative Scientific Research Program。
文摘Dual-atom catalysts(DACs) afford promising potential for oxygen reduction electrocatalysis due to their high atomic efficiency and high intrinsic activity.However,precise construction of dual-atom sites remains a challenge.In this work,a post-modification strategy is proposed to precisely fabricate DACs for oxygen reduction electrocatalysis.Concretely,a secondary metal precursor is introduced to the primary single-atom sites to introduce direct metal-metal interaction,which ensures the formation of desired atom pair structure during the subsequent pyrolysis process and allows for successful construction of DACs.The as-prepared FeCo-NC DAC exhibits superior oxygen reduction electrocatalytic activity with a half-wave potential of 0,91 V vs.reversible hydrogen electrode.Zn-air batteries equipped with the FeCo-NC DAC demonstrate higher peak power density than those with the Pt/C benchmark.More importantly,this post-modification strategy is demonstrated universal to achieve a variety of dual-atom sites.This work presents an effective synthesis methodology for precise construction of catalytic materials and propels their applications in energy-related devices.
基金supported by the National Natural Science Foundation of China(22234005,21974070)the Natural Science Foundation of Jiangsu Province(BK20222015)。
文摘Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utilization and exceptional catalytic functionality.Furthermore,accurately controlling atomic physical properties including spin,charge,orbital,and lattice degrees of atomically dispersed catalysts can realize the optimized chemical properties including maximum atom utilization efficiency,homogenous active centers,and satisfactory catalytic performance,but remains elusive.Here,through physical and chemical insight,we review and systematically summarize the strategies to optimize atomically dispersed ORR catalysts including adjusting the atomic coordination environment,adjacent electronic orbital and site density,and the choice of dual-atom sites.Then the emphasis is on the fundamental understanding of the correlation between the physical property and the catalytic behavior for atomically dispersed catalysts.Finally,an overview of the existing challenges and prospects to illustrate the current obstacles and potential opportunities for the advancement of atomically dispersed catalysts in the realm of electrocatalytic reactions is offered.
基金supported by the National Natural Science Foundation of China(22109100,22075203)Guangdong Basic and Applied Basic Research Foundation(2022A1515011677)+1 种基金Shenzhen Science and Technology Project Program(JCYJ2021032409420401)Natural Science Foundation of SZU(000002111605).
文摘The high-temperature pyrolysis process for preparing M–N–C single-atom catalyst usually results in high heterogeneity in product structure concurrently contains multiscale metal phases from single atoms(SAs),atomic clusters to nanoparticles.Therefore,understanding the interactions among these components,especially the synergistic effects between single atomic sites and cluster sites,is crucial for improving the oxygen reduction reaction(ORR)activity of M–N–C catalysts.Accordingly,herein,we constructed a model catalyst composed of both atomically dispersed FeN4 SA sites and adjacent Fe clusters through a site occupation strategy.We found that the Fe clusters can optimize the adsorption strength of oxygen reduction intermediates on FeN4 SA sites by introducing electron-withdrawing–OH ligands and decreasing the d-band center of the Fe center.The as-developed catalyst exhibits encouraging ORR activity with halfwave potentials(E1/2)of 0.831 and 0.905 V in acidic and alkaline media,respectively.Moreover,the catalyst also represents excellent durability exceeding that of Fe–N–C SA catalyst.The practical application of Fe(Cd)–CNx catalyst is further validated by its superior activity and stability in a metalair battery device.Our work exhibits the great potential of synergistic effects between multiphase metal species for improvements of singleatom site catalysts.
基金financially supported by the National Natural Science Foundation of China (51874197)the Natural Science Foundation of Shanghai (21ZR1429400,22ZR1429700)。
文摘Metal-free defective carbon materials with abundant active sites have been widely studied as low-cost and efficient oxygen reduction reaction(ORR)electrocatalysts in metal-air batteries.However,the active sites in defective carbon are easily subjected to serious oxidation or hydroxylation during ORR or storage,leading to rapid degradation of activity.Herein,we design a van der Waals heterostructure comprised of vitamin C(VC)and defective carbon(DC)to not only boost the activity but also enhance the durability and storage stability of the DC-VC electrocatalyst.The formation of VC van der Waals between DC and VC is demonstrated to be an effective strategy to protect the defect active sites from oxidation and hydroxylation degradation,thus significantly enhancing the electrochemical durability and storage anti-aging performance.Moreover,the DC-VC van der Waals can reduce the reaction energy barrier to facilitate the ORR.These findings are also confirmed by operando Fourier transform infrared spectroscopy and density functional theory calculations.It is necessary to mention that the preparation of this DC-VC electrocatalyst can be scaled up,and the ORR performance of the largely produced electrocatalyst is demonstrated to be very consistent.Furthermore,the DC-VC-based aluminum-air batteries display very competitive power density with good performance maintenance.
基金financially supported by the National Key R&D Program of China(2022YFB4004100)the National Natural Science Foundation of China(22272161)+6 种基金the Jilin Province Science and Technology Development Program(20230101367JC)financially supported by the National Natural Science Foundation of China(22073094)the Science and Technology Development Program of Jilin Province(20210402059GH)the Science and Technology Plan Projects of Yunnan Province(202101BC070001–007)the Major Science and Technology Projects for Independent Innovation of China FAW Group Co.,Ltd(20220301018GX)the essential support of the Network and Computing Center,CIAC,CASthe Computing Center of Jilin Province。
文摘Developing cost-effective,robust and stable non-precious metal catalysts for oxygen reduction reaction(ORR) is of paramount importance for electrochemical energy conversion devices such as fuel cells and metal-air batteries.Although Fe-N-C single atom catalysts(SACs) have been hailed as the most promising candidate due to the optimal binding strength of ORR intermediates on the Fe-N_(4) sites,they suffer from serious mass transport limitations as microporous templates/substrates,i.e.,zeolitic imidazolate frameworks(ZIFs),are usually employed to host the active sites.Motivated by this challenge,we herein develop a hydrogen-bonded organic framework(HOF)-assisted pyrolysis strategy to construct hierarchical micro/mesoporous carbon nanoplates for the deposition of atomically dispersed Fe-N_(4) sites.Such a design is accomplished by employing HOF nanoplates assembled from 2-aminoterephthalic acid(NH_(2)-BDC) and p-phenylenediamine(PDA) as both soft templates and C,N precursors.Benefitting from the structural merits inherited from HOF templates,the optimized catalyst(denoted as Fe-N-C SAC-950) displays outstanding ORR activity with a high half-wave potential of 0.895 V(vs.reversible hydrogen electrode(RHE)) and a small overpotential of 356 mV at 10 mA cm^(-2) for the oxygen evolution reaction(OER).More excitingly,its application potential is further verified by delivering superb rechargeability and cycling stability with a nearly unfading charge-discharge gap of 0.72 V after 160 h.Molecular dynamics(MD) simulations reveal that micro/mesoporous structure is conducive to the rapid mass transfer of O_(2),thus enhancing the ORR performance.In situ Raman results further indicate that the conversion of O_(2) to~*O_(2)-the rate-determining step(RDS) for Fe-N-C SAC-950.This work will provide a versatile strategy to construct single atom catalysts with desirable catalytic properties.
基金finically supported by the National Natural Science Foundation of China(22075055)the Guangxi Science and Technology Project(AB16380030)。
文摘Transition metal-nitrogen-carbon(M-N-C)as a promising substitute for the conventional noble metalbased catalyst still suffers from low activity and durability for oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs).To tackle the issue,herein,a new type of sulfur-doped ironnitrogen-hard carbon(S-Fe-N-HC)nanosheets with high activity and durability in acid media were developed by using a newly synthesized precursor of amide-based polymer with Fe ions based on copolymerizing two monomers of 2,5-thiophene dicarboxylic acid(TDA)as S source and 1,8-diaminonaphthalene(DAN)as N source via an amination reaction.The as-synthesized S-Fe-N-HC features highly dispersed atomic Fe Nxmoieties embedded into rich thiophene-S doped hard carbon nanosheets filled with highly twisted graphite-like microcrystals,which is distinguished from the majority of M-N-C with soft or graphitic carbon structures.These unique characteristics endow S-Fe-N-HC with high ORR activity and outstanding durability in 0.5 M H_(2)SO_(4).Its initial half-wave potential is 0.80 V and the corresponding loss is only 21 m V after 30,000 cycles.Meanwhile,its practical PEMFC performance is a maximum power output of 628.0 mW cm^(-2)and a slight power density loss is 83.0 m W cm^(-2)after 200-cycle practical operation.Additionally,theoretical calculation shows that the activity of Fe Nxmoieties on ORR can be further enhanced by sulfur doping at meta-site near FeN_(4)C.These results evidently demonstrate that the dual effect of hard carbon substrate and S doping derived from the precursor platform of amid-polymers can effectively enhance the activity and durability of Fe-N-C catalysts,providing a new guidance for developing advanced M-N-C catalysts for ORR.
基金support from the Natural Science Foundation of Shanghai (20ZR1464000)G.Zeng acknowledges the support from the National Natural Science Foundation of China (21878322,22075309)the Science and Technology Commission of Shanghai Municipality (19ZR1479200,22ZR1470100)。
文摘Metal-organic frameworks and covalent organic frameworks have been widely employed in electrochemical catalysis owing to their designable skeletons,controllable porosities,and well-defined catalytic centers.However,the poor chemical stability and low electron conductivity limited their activity,and single-functional sites in these frameworks hindered them to show multifunctional roles in catalytic systems.Herein,we have constructed novel metal organic polymers(Co-HAT-CN and Ni-HAT-CN)with dual catalytic centers(metal-N_(4) and metal-N_(2))to catalyze oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).By using different metal centers,the catalytic activity and selectivity were well-tuned.Among them,Co-HAT-CN catalyzed the ORR in a 4e^(-)pathway,with a half-wave potential of 0.8 V versus RHE,while the Ni-HAT-CN catalyze ORR in a 2e^(-)pathway with H_(2)O_(2) selectivity over 90%.Moreover,the Co-HAT-CN delivered an overpotential of 350 mV at 10 mA cm^(-2) with a corresponding Tafel slope of 24 mV dec^(-1) for OER in a 1.0 M KOH aqueous solution.The experimental results revealed that the activities toward ORR were due to the M-N_(4) sites in the frameworks,and both M-N_(4) and M-N_(2) sites contributed to the OER.This work gives us a new platform to construct bifunctional catalysts.
基金financially supported by the Natural Science Foundation of Shanxi Province(No.201901D111277)the National Natural Science Foundation of China(No.21571119)+1 种基金the Graduate Science and Technology Innovation Project Foundation of Shanxi Normal University(No.2021DCXM71)the Program for New Century Excellent Talents in University(No.NCET-12-1035)。
文摘metal oxide electronic interactions in composite electrocatalysts have a considerable impact on their catalytic capability.In this study,we successfully synthesized an electrocatalytic material composed of MoO_(3)/C speciessupported Pd nanoparticles(Pd-MoO_(3)/C)using a convenient hydrothermal method,which exhibited excellent catalytic activities for both ethanol oxidation and oxygen reduction in KOH media.The specific activity of PdMoO_(3)/C toward ethanol oxidation with MoO_(3)loading(40wt%)was~2.6 times greater than that for the commercial Pd/C(10 wt%)with the same Pd content.In particular,the activity could effectively hold up to~60%of its maximum activity after 500-cycle tests,demonstrating improved cyclical stability.Notably,the fast electron transfer kinetics toward oxygen reduction for Pd-MoO_(3)/C(40%)were also comparable to those of commercial Pt/C(20 wt%)catalysts.These superior electrochemical features are primarily derived from the stronger electronic coupling between Pd and MoO_(3)through charge transfer,which can supply more active centers and improve the anti-poisoning ability.Meanwhile,the MoO_(3)species in the Pd-MoO_(3)/C composite may provide additional benefits in terms of electrical conductivity and dispersion.
基金This work was supported by the National Natural Science Foundation of China(No.22102218)the Natural Science Foundation of Hunan Province(No.2020JJ4684)+1 种基金the science and technology innovation Program of Hunan Province(No.2022RC1110)the Open Sharing Fund for the Large-scale Instruments and Equipments of Central South University(No.CSUZC202221).
文摘The development of thermodynamically controllable synthetic strategy to manipulate the morphology of ZIF-8 without capping agent is essential to help understanding their facet effect and the structure-activity relationship of single atom catalysts derived from ZIF-8.Here,we prepared ZIF-8 with different morphologies(cube,truncated rhombododecahedral and rhombododecahedral)and thus area ratio of exposed{100},{110}facets by a thermodynamically controllable synthetic strategy.When the reaction proceeds under room temperature(30℃),the assembling of ZIF-8 followed an area-reducing layered growth mode,while switched to an integral layered growth mode at lower temperature-40℃.Moreover,this strategy also works to obtain ZIF-8 encapsulated with metal precursors(Fe(acac)_(3),Cu(acac)_(2)and Co(acac)_(2)).Single Fe atom anchored on nitrogen doped carbon catalysts(SA-Fe/CN)derived from Fe-ZIF-8 retain their original morphologies and the unsaturated surface-active sites on{100}facet,which further displays different catalytic performance towards oxygen reduction reaction(ORR).This work not only reveals the different growth pattern of ZIF-8,but also points out a new direction for designing and synthesizing MOFs with different morphology rationally.
基金supported by the National Natural Science Foundation of China(Nos.22179093 and 21905202)。
文摘Electrocatalytic oxygen reduction via a two-electron pathway(2e^(-)-ORR)is a promising and eco-friendly route for producing hydrogen peroxide(H_(2)O_(2)).Single-atom catalysts(SACs)typically show excellent selectivity towards 2e^(-)-ORR due to their unique electronic structures and geometrical configurations.The very low density of single-atom active centers,however,often leads to unsatisfactory H_(2)O_(2)yield rate,significantly inhibiting their practical feasibility.Addressing this,we herein introduce fluorine as a secondary doping element into conventional SACs,which does not directly coordinate with the singleatom metal centers but synergize with them in a remote manner.This strategy effectively activates the surrounding carbon atoms and converts them into highly active sites for 2e^(-)-ORR.Consequently,a record-high H_(2)O_(2)yield rate up to 27 mol g^(-1)h^(-1)has been achieved on the Mo–F–C catalyst,with high Faradaic efficiency of 90%.Density functional theory calculations further confirm the very kinetically facile 2e^(-)-ORR over these additional active sites and the superiority of Mo as the single-atom center to others.This strategy thus not only provides a high-performance electrocatalyst for 2e^(-)-ORR but also should shed light on new strategies to significantly increase the active centers number of SACs.
基金the financial support provided by the National Natural Science Foundation of China(22075290,21972068,52164028)the Beijing Natural Science Foundation(Z200012)+3 种基金the State Key Laboratory of Multiphase Complex Systemsthe Institute of Process Engineeringthe Chinese Academy of Sciences(MPCS-2021-A-05)the Nanjing IPE Institute of Green Manufacturing Industry(E0010725).
文摘Dealloying by which the transition metal is partially or completely leached from an alloy precursor is an effective way to optimize the fundamental effects for further enhancing the electrocatalysis of a catalyst.Herein,to address the deficiencies associated with the commonly used dealloying methods,for example,electrochemical and sulfuric acid/nitric acid treatment,we report an acetic acid-assisted mild strategy to dealloy Cu atoms from the outer surface layers of CuPd alloy nanoparticles to achieve high-efficiency electrocatalysis for oxygen reduction and ethanol oxidation in an alkaline electrolyte.The leaching of Cu atoms by acetic acid exerts an additional compressive strain effect on the surface layers and exposes more active Pd atoms,which is beneficial for boosting the catalytic performance of a dealloyed catalyst for the oxygen reduction reaction(ORR)and the ethanol oxidation reaction(EOR).In particular,for ORR,the CuPd nanoparticles with a Pd/Cu molar ratio of 2:1 after acetic dealloying show a half-wave potential of 0.912 V(vs.RHE)and a mass activity of 0.213 AmgPd^(-1) at 0.9 V,respectively,while for EOR,the same dealloyed sample has a mass activity and a specific activity of 8.4 Amg^(-1) and 8.23 mA cm^(-2),respectively,much better than their dealloyed counterparts at other temperatures and commercial Pd/C as well as a Pt/C catalyst.
基金supported by National Key R&D Prog ram of China (2022YFB3704900 and 2021YFF0500500)National Natural Science Foundation of China (22025504, 21621001, and 22105082)+4 种基金the SINOPEC Research Institute of Petroleum Processing"111"project (BP0719036 and B17020)China Postdoctoral Science Foundation (2020TQ0118 and 2020M681034)the program for JLU Science and Technology Innovative Research Teamthe Taishan Scholars Program (No. tsqn202211124)
文摘Metal-free carbon-based materials are considered as promising oxygen reduction reaction(ORR)electrocatalysts for clean energy conversion,and their highly dense and exposed carbon active sites are crucial for efficient ORR.In this work,two unique quasi-three-dimensional cyclotriphosphazene-based covalent organic frameworks(Q3CTP-COFs)and their nanosheets were successfully synthesized and applied as ORR electrocatalysts.The abundant electrophilic structure in Q3CTP-COFs induces a high density of carbon active sites,and the unique bilayer stacking of[6+3]imine-linked backbone facilitates the exposure of active carbon sites and accelerates mass diffusion during ORR.In particular,bulk Q3CTP-COFs can be easily exfoliated into thin COF nanosheets(NSs)due to the weak interlayerπ-πinteractions.Q3CTP-COF NSs exhibit highly efficient ORR catalytic activity(half-wave potential of 0.72 V vs.RHE in alkaline electrolyte),which is one of the best COF-based ORR electrocatalysts reported so far.Furthermore,Q3CTP-COF NSs can serve as a promising cathode for Zn-air batteries(delivered power density of 156 mW cm-2 at 300 mA cm^(-2)).This judicious design and accurate synthesis of such COFs with highly dense and exposed active sites and their nanosheets will promote the development of metal-free carbon-based electrocatalysts.
基金Higher Education Discipline Innovation Project,Grant/Award Number:D17007Xinxiang Major Science and Technology Projects,Grant/Award Number:21ZD001+1 种基金Henan Center for Outstanding Overseas Scientists,Grant/Award Number:GZS2022017National Natural Science Foundation of China,Grant/Award Numbers:51872075,51922008,52072114。
文摘Rational design of hierarchically structured electrocatalysts is particularly important for electrocatalytic oxygen reduction reaction(ORR).Here,ZIF-67 crystals are stringed on core-shell Ag@C nanocables using a coordinationmodulated process.Upon pyrolysis,Ag@C strings of Co nanoparticles embedded with three-dimensional porous carbon with beads-on-string hierarchical structures are developed.Due to the advantages of the rich electrochemical active sites of Co-based“beads”and the efficient electron transfer pathways via Ag@C“strings,”the resultant NH_(3)-Ag@C@Co-N-C-700 catalyst shows an improved electrocatalytic activity toward ORR.NH_(3)-Ag@C@Co-N-C-700 shows a high onset potential of 0.99 V versus RHE,a high half-wave potential of 0.88 V versus RHE,and a large limiting current of 5.8 mA cm^(-2),which are better than those of commercial Pt/C electrocatalysts.Additionally,the NH_(3)-Ag@C@Co-N-C-700 catalyst shows high stability and preeminent methanol tolerance,which makes NH_(3)-Ag@C@Co-N-C-700 a promising catalyst for oxygen electrocatalysis in fuel cell applications.