The manipulation of rectifying contact of Co and nitrogen-doped carbon hierarchical superstructures toward high-performance oxygen reduction reaction

Rational design and construction of oxygen reduction reaction(ORR)electrocatalysts with high activity,good stability,and low price are essential for the practical applications of renewable energy conversion devices,such as metal-air batteries.Electronic modification through constructing metal/semiconductor Schottky heterointerface represents a powerful strategy to enhance the electrochemical performance.Herein,we demonstrate a concept of Schottky electrocatalyst composed of uniform Co nanoparticles in situ anchored on the carbon nanotubes aligned on the carbon nanosheets(denoted as Co@N-CNTs/NSs hereafter)toward ORR.Both experimental findings and theoretical simulation testify that the rectifying contact could impel the voluntary electron flow from Co to N-CNTs/NSs and create an internal electric field,thereby boosting the electron transfer rate and improving the intrinsic activity.As a consequence,the Co@N-CNTs/NSs deliver outstanding ORR activity,impressive long-term durability,excellent methanol tolerance,and good performance as the air-cathode in the Zn-air batteries.The design concept of Schottky contact may provide the innovational inspirations for the synthesis of advanced catalysts in sustainable energy conversion fields.

Oxidation Evolution and Activity Origin of N-Doped Carbon in the Oxygen Reduction Reaction

N-doped carbon materials,with their applications as electrocatalysts for the oxygen reduction reaction(ORR),have been extensively studied.However,a negletcted fact is that the operating potential of the ORR is higher than the theoretical oxida-tion potential of carbon,possibly leading to the oxidation of carbon materials.Consequently,the infl uence of the structural oxidation evolution on ORR performance and the real active sites are not clear.In this study,we discover a two-step oxida-tion process of N-doped carbon during the ORR.The fi rst oxidation process is caused by the applied potential and bubbling oxygen during the ORR,leading to the oxidative dissolution of N and the formation of abundant oxygen-containing functional groups.This oxidation process also converts the reaction path from the four-electron(4e)ORR to the two-electron(2e)ORR.Subsequently,the enhanced 2e ORR generates oxidative H_(2)O_(2),which initiates the second stage of oxidation to some newly formed oxygen-containing functional groups,such as quinones to dicarboxyls,further diversifying the oxygen-containing functional groups and making carboxyl groups as the dominant species.We also reveal the synergistic eff ect of multiple oxygen-containing functional groups by providing additional opportunities to access active sites with optimized adsorption of OOH*,thus leading to high effi ciency and durability in electrocatalytic H_(2)O_(2) production.

Pyrolysis of Copper Phthalocyanine as Non-noble Metal Electrocatalysts for Oxygen Reduction Reaction

We investigated the relationship between oxygen reduction reaction(ORR)activity and the pyrolysis temperature(650-850℃)of CuPc in alkaline solution.The highly active sites were formed through the decomposition of CuPc or Cu-N_(4) structure after releasing 4-nitrophthalonitrile.Cu-Nx incorporated with carbon were the main active sites.The XPS measurement results show that,at lower temperature,the contents of pyridinic-N and pyrrolic-N account for the most of the total N.As the temperature is higher than 750℃,the content of graphitic N(26.11%)increases and pyridinic-N(58.81%)becomes the dominant specie.When the temperature is higher than 850℃,the content of graphitic N increases remarkably and becomes the dominant species.Moreover,the specific surface areas decrease with increased pyrolysis temperature.Benefiting from the synergistic effect,the pyrolysis temperature at 750℃of CuPc displays superior electrocatalytic properties.The obtained results reveal that the fabricated non-noble metal catalysts can be used as low-cost,efficient catalyst for water splitting ORR in metal-air batteries and fuel cells.

Deciphering the linear relationship in the activity of the oxygen reduction reaction on Pt electrodes:A decisive role of adsorbates

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.

Sulfur doped iron-nitrogen-hard carbon nanosheets as efficient and robust noble metal-free catalysts for oxygen reduction reaction in PEMFC

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.

Atomically dispersed Mn-N_(x) catalysts derived from Mn-hexamine coordination frameworks for oxygen reduction reaction

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.

Rational design of vitamin C/defective carbon van der Waals heterostructure for enhanced activity,durability and storage stability toward oxygen reduction reaction

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.

Atomically dispersed Fe sites on hierarchically porous carbon nanoplates for oxygen reduction reaction

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.

Healing the structural defects of spinel MnFe_(2)O_(4) to enhance the electrocatalytic activity for oxygen reduction reaction

Spinel metal oxides containing Mn,Co,or Fe(AB_(2)O_(4),A/B=Mn/Fe/Co)are one of the most promising nonPt electrocatalysts for oxygen reduction reaction(ORR)in alkaline conditions.However,the low conductivity of metal oxides and the poor intrinsic activities of transition metal sites lead to unsatisfactory ORR performance.In this study,eutectic molten salt(EMS)treatment is employed to reconstruct the atomic arrangement of MnFe_(2)O_(4)electrocatalyst as a prototype for enhancing ORR performance.Comprehensive analyses by using XAFS,soft XAS,XPS,and electrochemical methods reveal that the EMS treatment reduces the oxygen vacancies and spinel inverse in MnFe_(2)O_(4)effectively,which improves the electric conductivity and increases the population of more catalytically active Mn^(2+)sites with tetrahedral coordination.Moreover,the enhanced Mn-O interaction after EMS treatment is conducive to the adsorption and activation of O_(2),which promotes the first electron transfer step(generally considered as the ratedetermining step)of the ORR process.As a result,the EMS treated MnFe_(2)O_(4)catalyst delivers a positive shift of 40 mV in the ORR half-wave potential and a two-fold enhanced mass/specific activity.This work provides a convenient approach to manipulate the atomic architecture and local electronic structure of spinel oxides as ORR electrocatalysts and a comprehensive understanding of the structureperformance relationship from the molecular/atomic scale.

Boric Acid-Assisted Pyrolysis for High-Loading Single-Atom Catalysts to Boost Oxygen Reduction Reaction in Zn-Air Batteries

The emerging of single-atom catalysts(SACs)offers a great opportunity for the development of advanced energy storage and conversion devices due to their excellent activity and durability,but the actual mass production of high-loading SACs is still challenging.Herein,a facile and green boron acid(H_(3)BO_(3))-assisted pyrolysis strategy is put forward to synthesize SACs by only using chitosan,cobalt salt and H_(3)BO_(3)as precursor,and the effect of H_(3)BO_(3)is deeply investigated.The results show that molten boron oxide derived from H_(3)BO_(3)as ideal high-temperature carbonization media and blocking media play important role in the synthesis process.As a result,the acquired Co/N/B tri-doped porous carbon framework(Co-N-B-C)not only presents hierarchical porous structure,large specific surface area and abundant carbon edges but also possesses high-loading single Co atom(4.2 wt.%),thus giving rise to outstanding oxygen catalytic performance.When employed as a catalyst for air cathode in Zn-air batteries,the resultant Co-N-B-C catalyst shows remarkable power density and long-term stability.Clearly,our work gains deep insight into the role of H_(3)BO_(3)and provides a new avenue to synthesis of high-performance SACs.

Fe-N-C core-shell catalysts with single low-spin Fe(Ⅱ)-N_(4)species for oxygen reduction reaction and high-performance proton exchange membrane fuel cells

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.

Tuning Structural and Electronic Configuration of FeN_(4) via External S for Enhanced Oxygen Reduction Reaction

The Fe-N-C material represents an attractive oxygen reduction reaction electrocatalyst,and the FeN_(4)moiety has been identified as a very competitive catalytic active site.Fine tuning of the coordination structure of FeN_(4)has an essential impact on the catalytic performance.Herein,we construct a sulfur-modified Fe-N-C catalyst with controllable local coordination environment,where the Fe is coordinated with four in-plane N and an axial external S.The external S atom affects not only the electron distribution but also the spin state of Fe in the FeN_(4)active site.The appearance of higher valence states and spin states for Fe demonstrates the increase in unpaired electrons.With the above characteristics,the adsorption and desorption of the reactants at FeN_(4)active sites are optimized,thus promoting the oxygen reduction reaction activity.This work explores the key point in electronic configuration and coordination environment tuning of FeN_(4)through S doping and provides new insight into the construction of M-N-C-based oxygen reduction reaction catalysts.

Engineering asymmetric electronic structure of cobalt coordination on CoN_(3)S active sites for high performance oxygen reduction reaction

The efficacy of the oxygen reduction reaction(ORR) in fuel cells can be significantly enhanced by optimizing cobalt-based catalysts,which provide a more stable alternative to iron-based catalysts.However,their performance is often impeded by weak adsorption of oxygen species,leading to a 2e^(-)pathway that negatively affects fuel cell discharge efficiency.Here,we engineered a high-density cobalt active center catalyst,coordinated with nitrogen and sulfur atoms on a porous carbon substrate.Both experimental and theoretical analyses highlighted the role of sulfur atoms as electron donors,disrupting the charge symmetry of the original Co active center and promoting enhanced interaction with Co 3d orbitals.This modification improves the adsorption of oxygen and reaction intermediates during ORR,significantly reducing the production of hydrogen peroxide(H_(2)O_(2)).Remarkably,the optimized catalyst demonstrated superior fuel cell performance,with peak power densities of 1.32 W cm^(-2) in oxygen and 0.61 W cm^(-2) in air environments,respectively.A significant decrease in H_(2)O_(2) by-product accumulation was observed during the reaction process,reducing catalyst and membrane damage and consequently improving fuel cell durability.This study emphasizes the critical role of coordination symmetry in Co/N/C catalysts and proposes an effective strategy to enhance fuel cell performance.

Exploring the contribution of oxygen reduction reaction to Mg corrosion by modeling assisted local analysis

Oxygen reduction reaction(ORR)has been disclosed in recent studies as a significant secondary cathodic process during magnesium corrosion.This work elaborates on the contribution of ORR to the total corrosion process of pure Mg at different impurity levels in NaCl electrolyte with the assistance of local techniques.A finite element based numerical model taking into account the contribution of ORR during the corrosion of the Mg test materials has been designed in this study considering the local oxygen concentration.Respective computational simulations were calibrated based on the experimental data and evaluated accordingly.Finally,the simultaneous monitoring of local concentration of H_(2) and O_(2),and the combined modeling study reveal the relation between ORR and hydrogen evolution reaction.

Strong synergy between physical and chemical properties:Insight into optimization of atomically dispersed oxygen reduction catalysts

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.

Oxygen‑Coordinated Single Mn Sites for Efficient Electrocatalytic Nitrate Reduction to Ammonia

Electrocatalytic nitrate reduction reaction has attracted increasing attention due to its goal of low carbon emission and environmental protection.Here,we report an efficient NitRR catalyst composed of single Mn sites with atomically dispersed oxygen(O)coordination on bacterial cellulose-converted graphitic carbon(Mn-O-C).Evidence of the atomically dispersed Mn-(O-C_(2))_(4)moieties embedding in the exposed basal plane of carbon surface is confirmed by X-ray absorption spectroscopy.As a result,the as-synthesized Mn-O-C catalyst exhibits superior NitRR activity with an NH_(3)yield rate(RNH_(3))of 1476.9±62.6μg h^(−1)cm^(−2)at−0.7 V(vs.reversible hydrogen electrode,RHE)and a faradaic efficiency(FE)of 89.0±3.8%at−0.5 V(vs.RHE)under ambient conditions.Further,when evaluated with a practical flow cell,Mn-O-C shows a high RNH_(3)of 3706.7±552.0μg h^(−1)cm^(−2)at a current density of 100 mA cm−2,2.5 times of that in the H cell.The in situ FT-IR and Raman spectroscopic studies combined with theoretical calculations indicate that the Mn-(O-C_(2))_(4)sites not only effectively inhibit the competitive hydrogen evolution reaction,but also greatly promote the adsorption and activation of nitrate(NO_(3)^(−)),thus boosting both the FE and selectivity of NH_(3)over Mn-(O-C_(2))_(4)sites.

Improving the Efficiency of Water Splitting and Oxygen Reduction Via Single-Atom Anchoring on Graphyne Support

Single-atom catalysts(SACs)have received significant interest for optimizing metal atom utilization and superior catalytic performance in hydrogen evolution reaction(HER),oxygen evolution reaction(OER),and oxygen reduction reaction(ORR).In this study,we investigate a range of single-transition metal(STM_(1)=Sc_(1),Ti_(1),V_(1),Cr_(1),Mn_(1),Fe_(1),Co_(1),Ni_(1),Cu_(1),Zr_(1),Nb_(1),Mo_(1),Ru_(1),Rh_(1),Pd_(1),Ag_(1),W_(1),Re_(1),Os_(1),Ir_(1),Pt_(1),and Au_(1))atoms supported on graphyne(GY)surface for HER/OER and ORR using first-principle calculations.Ab initio molecular dynamics(AIMD)simulations and phonon dispersion spectra reveal the dynamic and thermal stabilities of the GY surface.The exceptional stability of all supported STM_(1)atoms within the H1 cavity of the GY surface exists in an isolated form,facilitating the uniform distribution and proper arrangement of single atoms on GY.In particular,Sc_(1),Co_(1),Fe_(1),and Au_(1)/GY demonstrate promising catalytic efficiency in the HER due to idealisticΔG_(H^(*))values via the Volmer-Heyrovsky pathway.Notably,Sc_(1)and Au_(1)/GY exhibit superior HER catalytic activity compared to other studied catalysts.Co_(1)/GY catalyst exhibits higher selectivity and activity for the OER,with an overpotential(0.46 V)comparable to MoC_(2),IrO_(2),and RuO_(2).Also,Rh_(1)and Co_(1)/GY SACs exhibited promising electrocatalysts for the ORR,with an overpotential of 0.36 and0.46 V,respectively.Therefore,Co_(1)/GY is a versatile electrocatalyst for metal-air batteries and water-splitting.This study further incorporates computational analysis of the kinetic potential energy barriers of Co_(1)and Rh_(1)in the OER and ORR.A strong correlation is found between the estimated kinetic activation barriers for the thermodynamic outcomes and all proton-coupled electron transfer steps.We establish a relation for the Gibbs free energy of intermediates to understand the mechanism of SACs supported on STM,/GY and introduce a key descriptor.This study highlights GY as a favorable single-atom support for designing highly active and cost-effective versatile electrocatalysts for practical applications.

Modulation of Electronic States in Bimetallic-doped Nitrogen-Carbon Based Nanoparticles for Enhanced Oxygen Reduction Kinetics

Controlling the local electronic structure of active ingredients to improve the adsorption desorption characteristics of oxygen-containing intermediates over the electrochemical liquid-solid interfaces is a critical challenge in the field of oxygen reduction reaction(ORR)catalysis.Here,we offer a simple approach for modulating the electronic states of metal nanocrystals by bimetal co-doping into carbon-nitrogen substrate,allowing us to modulate the electronic structure of catalytic active centers.To test our strategy,we designed a typical bimetallic nanoparticle catalyst(Fe-Co NP/NC)to flexibly alter the reaction kinetics of ORR.Our results from synchrotron Xray absorption spectroscopy and X-ray photoelectron spectroscopy showed that the co-doping of iron and cobalt could optimize the intrinsic charge distribution of Fe-Co NP/NC catalyst,promoting the oxygen reduction kinetics and ultimately achieving remarkable ORR activity.Consequently,the carefully designed Fe-Co NP/NC exhibits an ultra-high kinetic current density at the operating voltage(71.94 mA/cm^(2)at 0.80 V),and the half-wave potential achieves 0.915 V,which is obviously better than that of the corresponding controls including Fe NP/NC,Co NP/NC.Our findings provide a unique perspective for optimizing the electronic structure of active centers to achieve higher ORR catalytic activity and faster kinetics.

Tin-mediated carbon-confined Pt_(3)Co ordered intermetallic nanoparticles as highly efficient and durable oxygen reduction electrocatalysts for rechargeable zinc-air batteries

The development of electrocatalysts for the oxygen reduction reaction(ORR) that bears high selectivity,exceptional activity,and long-term stability is crucial for advancing various green energy technologies.Intermetallics composed of platinum and transition metals are considered to be promising candidates for this purpose.However,they typically face challenges such as unfavorable intrinsic activity and a propensity for particle aggregation,diminishing their ORR performance.Against this backdrop,we present our findings on a N-doped carbon confined Pt_(3)Co intermetallic doped with p-block metal tin(Pt_(3)Co_(x)Sn_(1-x)/NC).The introduction of Sn induces lattice strain due to its larger atomic size,which leads to the distortion of the Pt_(3)Co lattice structure,while the coupling of carbon polyhedra inhibits the particle aggregation.The optimized Pt_(3)Co_(0.8)Sn_(0.2)/NC catalyst demonstrates an impressive half-wave potential of 0.86 V versus RHE,surpassing both Pt_(3)Co/NC and Pt_(3)Sn/NC catalysts.Moreover,the Pt_(3)Co_(0.8)Sn_(0.2)/NC exhibits a mass-specific activity as high as 1.4 A mg_(Pt)^(-1),ranking it in the top level among the intermetallicsbased ORR electrocatalysts.When further employed as a cathode material in a self-assembled zinc-air battery,it shows stable operation for over 80 h.These results underscore the significant impact of lattice strain engineering through the strategic doping of p-block metal in the carbon-confined Pt_(3)Co intermetallic,thereby enhancing the catalytic efficiency for the ORR.

Boosting the Oxygen Reduction Performance of Fe-N-C Catalyst Using Zeolite as an Oxygen Reservoir

Non-precious metal electrocatalysts(such as Fe-N-C materials) for the oxygen(O_(2)) reduction reaction demand a high catalyst loading in fuel cell devices to achieve workable performance. However, the extremely low solubility of O_(2) in water creates severe mass transport resistance in the thick catalyst layer of Fe-N-C catalysts. Here, we introduce silicalite-1 nanocrystals with hydrophobic cavities as sustainable O_(2) reservoirs to overcome the mass transport issue of Fe-N-C catalysts. The extra O_(2) supply to the adjacent catalysts significantly alleviated the negative effects of the severe mass transport resistance. The hybrid catalyst(Fe-N-C@silicalite-1) achieved a higher limiting current density than Fe-N-C in the half-cell test. In the H_(2)-O_(2) and H_2-air proton exchange membrane fuel cells, Fe-N-C@silicalite-1 exhibited a 16.3% and 20.2% increase in peak power density compared with Fe-N-C, respectively. The O_(2)-concentrating additive provides an effective approach for improving the mass transport imposed by the low solubility of O_(2) in water.