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
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
Covalent organic frameworks(COFs)have emerged as a class of promising supports for electrocatalysis because of their advantages including good crystallinity,highly ordered pores,and structural diversity.However,their ...Covalent organic frameworks(COFs)have emerged as a class of promising supports for electrocatalysis because of their advantages including good crystallinity,highly ordered pores,and structural diversity.However,their poor conductivity represents the main obstruction to their practical application.Here,we reported a novel synthesis strategy for synergistically endowing a triphenylamine-based COFs with improved electrical conductivity and excellent catalytic activity for oxygen reduction,via the in-situ redox deposition and confined growth of palladium nanoparticles inside the porous structure of COFs using reductive triphenylamine frameworks as reducing agent;meanwhile,the triphenylamine unit was oxidized to radical cation structure and affords radical cation COFs with conductivity as high as3.2*10^(-1) S m^(-1).Such a uniform confine palladium nanoparticle on highly conductive COFs makes it an efficient electrocatalyst for four-electron oxygen reduction reaction(4e-ORR),showing excellent activities and fast kinetics with a remarkable half-wave potential(E_(1/2))of 0.865 V and an ultralow Tafel slope of 39.7 mV dec^(-1) in alkaline media even in the absence of extra commercial conductive fillers.The generality of this strategy was proved by preparing the different metal and metal alloy nanoparticles supported on COFs(Au@COF,Pt@COF,AuPd@COF,AgPd@COF,and PtPd@COF)using reductive triphenylamine frameworks as reducing agent.This work not only provides a facile strategy for the fabrication of highly conductive COF supported ORR electrocatalysts,but also sheds new light on the practical application of Zn-air battery.展开更多
Electrocatalytic oxygen reduction and evolution reactions are involved in new energy conversion and storage technologies,such as various fuel cells and metal-air batteries and also water splitting devices[1,2].However...Electrocatalytic oxygen reduction and evolution reactions are involved in new energy conversion and storage technologies,such as various fuel cells and metal-air batteries and also water splitting devices[1,2].However,both reactions are very slow in kinetics,and thus catalysts are required[3,4].展开更多
Defect-engineered carbon materials have been emerged as promising electrocatalysts for oxygen reduction reaction(ORR)in metal-air batteries.Developing a facile strategy for the preparation of highly active nanocarbon ...Defect-engineered carbon materials have been emerged as promising electrocatalysts for oxygen reduction reaction(ORR)in metal-air batteries.Developing a facile strategy for the preparation of highly active nanocarbon electrocatalysts remains challenging.Herein,a low-cost and simple route is developed to synthesize defective graphene by pyrolyzing the mixture of glucose and carbon nitride.Molecular dynamics simulations reveal that the graphene formation is ascribed to two-dimensional layered feature of carbon nitride,and high compatibility of carbon nitride/glucose systems.Structural measurements suggest that the graphene possesses rich edge and topological defects.The graphene catalyst exhibits higher power density than commercial Pt/C catalyst in a primary Zn-air battery.Combining experimental results and theoretical thermodynamic analysis,it is identified that graphitic nitrogen-modified topological defects at carbon framework edges are responsible for the decent ORR performance.The strategy presented in this work can be can be scaled up readily to fabricate defective carbon materials.展开更多
The electrochemical reduction of carbon dioxide offers a sound and economically viable technology for the electrification and decarbonization of the chemical and fuel industries.In this technology,an electrocatalytic ...The electrochemical reduction of carbon dioxide offers a sound and economically viable technology for the electrification and decarbonization of the chemical and fuel industries.In this technology,an electrocatalytic material and renewable energy-generated electricity drive the conversion of carbon dioxide into high-value chemicals and carbon-neutral fuels.Over the past few years,single-atom catalysts have been intensively studied as they could provide near-unity atom utilization and unique catalytic performance.Single-atom catalysts have become one of the state-of-the-art catalyst materials for the electrochemical reduction of carbon dioxide into carbon monoxide.However,it remains a challenge for single-atom catalysts to facilitate the efficient conversion of carbon dioxide into products beyond carbon monoxide.In this review,we summarize and present important findings and critical insights from studies on the electrochemical carbon dioxide reduction reaction into hydrocarbons and oxygenates using single-atom catalysts.It is hoped that this review gives a thorough recapitulation and analysis of the science behind the catalysis of carbon dioxide into more reduced products through singleatom catalysts so that it can be a guide for future research and development on catalysts with industry-ready performance for the electrochemical reduction of carbon dioxide into high-value chemicals and carbon-neutral fuels.展开更多
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.Intermetal...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.展开更多
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 c...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.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
The growth of electrochemically inert segregation layers on the surface of solid oxide fuel cell cathodes has become a bottleneck restricting the development of perovskite-structured oxygen reduction catalysts.Here,we...The growth of electrochemically inert segregation layers on the surface of solid oxide fuel cell cathodes has become a bottleneck restricting the development of perovskite-structured oxygen reduction catalysts.Here,we report a new discovery in which enriched Ba and Fe ions on the near-surface of Nd_(1/2)Ba_(1/2)Co_(1/3)Fe_(1/3)Mn_(1/3)O_(3-δ)spontaneously agglomerate into dispersed Ba_(5)Fe_(2)O_(8) nanoparticles and maintain a highly active and durable perovskite structure on the surface.This unique surface selfcleaning phenomenon is related to the low average potential energy of Ba_(5)Fe_(2)O_(8),which is grown on the near-surface layer.The electrochemically inert Ba_(5)Fe_(2)O_(8) segregation layer on the near-surface of the perovskite catalyst achieves self-cleaning by regulating the formation energy of enriched metal oxides.This self-cleaned perovskite surface exhibits an ultrafast oxygen exchange rate,high catalytic activity for the oxygen reduction reaction,and good adaptability to the actual working conditions of solid oxide fuel cell stacks.This study paves a new way for overcoming the stubborn problem of perovskite catalyst surface deactivation and enriches the scientific knowledge of surface catalysis.展开更多
Developing high efficient Pd-based electrocatalysts for oxygen reduction reaction(ORR) is still challenging for alkaline membrane fuel cell,since the strong oxygen adsorption energy and easy agglomerative intrinsic pr...Developing high efficient Pd-based electrocatalysts for oxygen reduction reaction(ORR) is still challenging for alkaline membrane fuel cell,since the strong oxygen adsorption energy and easy agglomerative intrinsic properties. In order to simultaneously solve these problems, Pd/Co_(3)O_(4)–N–C multidimensional materials with porous structures is designed as the ORR catalysts. In details, the ZIF-67 with polyhedral structure was firstly synthesized and then annealed at high-temperature to prepare the N-doped Co_(3)O_(4)carbon-based material, which was used to homogeneously confine Pd nanoparticles and obtained the Pd/Co_(3)O_(4)–N–C series catalysts. The formation of Co–N and C–N bond could provide efficient active sites for ORR. Simultaneously, the strong electronic interaction in the interface between the Pd and N-doped Co_(3)O_(4)could disperse and avoid the agglomeration of Pd nanoparticles and ensure the exposure of active sites, which is crucial to lower the energy barrier toward ORR and substantially enhance the ORR kinetics. Hence, the Pd/Co_(3)O_(4)–N–C nanocompounds exhibited excellent ORR catalytic performance, ideal Pd mass activity, and durability in 0.1 mol L-1KOH solution compared with Co_(3)O_(4)–N–C and Pd/C. The scalable synthesis method, relatively low cost, and excellent electrochemical ORR performance indicated that the obtained Pd/Co_(3)O_(4)–N–C electrocatalyst had the potential for application on fuel cells.展开更多
Ruthenium(Ru)is an attractive potential alternative to platinum as an electrocatalyst for the oxygen reduction reaction(ORR),in virtue of its high catalytic selectivity and relatively low price.In this work,a series o...Ruthenium(Ru)is an attractive potential alternative to platinum as an electrocatalyst for the oxygen reduction reaction(ORR),in virtue of its high catalytic selectivity and relatively low price.In this work,a series of well-dispersed nitrogen-coordinated Ru-clusters on carbon black(Ru_(x)N_(y)/C)were prepared by pyrolyzing different Ru-containing sandwich compounds as the Ru sources.The higher thermal stability of these complexed sandwich precursors(bis(1,2,3,4,5-pentamethylcyclopentadienyl)Ru(II)monomer,dichloro(p-cymene)Ru(II)dimer,and chloro(1,2,3,4,5-pentamethylcyclopentadienyl)Ru(II)tetramer)affords the control of coordinated state for the resulting Ru-clusters,in comparison of that derived from ruthenium chlorides.After the pyrolysis treatment,the Ru coordinated state in Ru_(x)N_(y)/C,with the Ru–N and Ru–Ru bonds,still showed the structural inheritance from the Ru(II)monomer,dimer,and tetramer,but using ruthenium chlorides as the Ru source resulted in the nanoscale Ru agglomerations.The ORR testing exhibited that the Ru_(x)N_(y)/C sample derived from the Ru(II)tetramer(Ru_(x)N_(y)/C-T)presents the higher catalytic activity than the other obtained samples in either alkaline or acidic electrolytes.Even in the acidic electrolyte,Ru_(x)N_(y)/C-T shows the comparable ORR activity to that of Pt/C catalysts,and it shows the superior tolerance against methanol and CO.The X-ray absorption spectroscopy and density functional theory calculations demonstrate that these tetra-nuclear Ru-clusters could be the most active site due to their broadened d-orbital bands and lower energy d-band center than those of other subnano species and nanocrystals,and their favorable Yeager-type adsorption of O_(2)-molecules is also contributed to promoting O–O bond cleavage and accelerating the ORR process.展开更多
Platinum(Pt)-based materials are still the most efficient and practical catalysts to drive the sluggish kinetics of cathodic oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs).However,their c...Platinum(Pt)-based materials are still the most efficient and practical catalysts to drive the sluggish kinetics of cathodic oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs).However,their catalysis and stability performance still need to be further improved in terms of corrosion of both carbon support and Pt catalyst particles as well as Pt loading reduction.Based on the developed synthetic strategies of alloying/nanostructuring Pt particles and modifying/innovating supports in developing conventional Pt-based catalysts,Pt single-atom catalysts(Pt SACs)as the recently burgeoning hot materials with a potential to achieve the maximum utilization of Pt are comprehensively reviewed in this paper.The design thoughts and synthesis of various isolated,alloyed,and nanoparticlecontained Pt SACs are summarized.The single-atomic Pt coordinating with non-metals and alloying with metals as well as the metal-support interactions of Pt single-atoms with carbon/non-carbon supports are emphasized in terms of the ORR activity and stability of the catalysts.To advance further research and development of Pt SACs for viable implementation in PEMFCs,various technical challenges and several potential research directions are outlined.展开更多
Core-shell nanostructures have been widely investigated to improve the electrocatalytic perfor-mance of platinum. However, organic precursors, surfactants or high temperature are usually nec-essary during the prepa...Core-shell nanostructures have been widely investigated to improve the electrocatalytic perfor-mance of platinum. However, organic precursors, surfactants or high temperature are usually nec-essary during the preparation procedure. Unfortunately, these requirements limit the application of these methods on a large scale. Herein, a Pdcore@ Pt shell nanostructure was fabricated through the reduction of fcPtCU by dissociated hydrogen at room temperature without the assistance o f either a surfactant or a high-boiling point solvent. The shell thickness of this nanostructure was successfully controlled by varying the amount of fcPtCU; core-shell nanoparticles with a shell thickness of 0.45, 0.75 and 0.90 nm w ere obtained, as determined by TEM. The remarkable crystallinity and epitaxial growth of the Pdcore@ Pt shell nanostructure were revealed by HRTEM and EDS. According to ICP and XPS, surface segregation of Pt was established. The impressive ORR performance was attributed to the weak adsorption strength of the OHads species, which resulted from the electron transfer impact between the Pdcore and Ptshell. The facile and clean preparation method can be used to prepare other core-shell nanostructures under a mild atmosphere.展开更多
Nanoporous Pd and binary Pd-Cu particles were prepared by a hydrothermal method using ethylene glycol as a reduction agent and they were directly immobilized on Ti substrates named as Ti-supported Pd-based catalysts. ...Nanoporous Pd and binary Pd-Cu particles were prepared by a hydrothermal method using ethylene glycol as a reduction agent and they were directly immobilized on Ti substrates named as Ti-supported Pd-based catalysts. Their electrocatalytic activity for formic acid oxidation and oxygen reduction reaction (ORR) in alkaline media was examined by voltammetric techniques. Among the as-prepared catalysts, nanoPdslCu19/Ti catalyst presents the highest current density of 39.8 mA/cm2 at -0.5 V or 66.4 mA/cm2 at -0.3 V for formic acid oxidation. The onset potential of ORR on the nanoPdslCU19/Ti catalyst presents an about 70 mV positive shift compared to that on the nanoPd/Ti, and the current density of ORR at -0.3 V is 2.12 mA/cm2, which is 3.7 times larger than that on the nanoPd/Ti.展开更多
With the rapid development of society and economy, the excessive consumption of fossil energy has led to the global energy and environment crisis. In order to explore the sustainable development of new energy, researc...With the rapid development of society and economy, the excessive consumption of fossil energy has led to the global energy and environment crisis. In order to explore the sustainable development of new energy, research based on electrocatalysis has attracted extensive attention in the academic circle. The main challenge in this field is to develop nano-catalysts with excellent electrocatalytic activity and selectivity for target products. The state of the active site in catalyst plays a decisive role in the activity and selectivity of the reaction. In order to design efficient and excellent catalysts, it is an effective means to adjust the electronic structure of catalysts. Electronic effects are also called ligand effects. By alloying with rare earth(RE) elements, electrons can be redistributed between RE elements and transition metal elements, achieving accurate design of the electronic structure of the active site in the alloy. Because of the unique electronic structure of RE, it has been paid attention in the field of catalysis. The outermost shell structure of RE elements is basically the same as that of the lower shell, except that the number of electrons in the 4f orbital is different, but the energy level is similar, so their properties are very similar. When RE elements form compounds, both the f electrons in the outermost shell and the d electrons in the lower outer shell can participate in bonding. In addition, part of the 4f electrons in the third outer shell can also participate in bonding.In order to improve the performance of metal catalysts, alloying provides an effective method to design advanced functional materials. RE alloys can integrate the unique electronic structure and catalytic behavior of RE elements into metal materials, which not only provides an opportunity to adjust the electronic structure and catalytic activity of the active component, but also enhances the structural stability of the alloy and is expected to significantly improve the catalytic performance of the catalyst. From the perspective of electronic and catalytic activity, RE elements have unique electronic configuration and lanthanide shrinkage effect. Alloying with RE elements will make the alloy have more abundant electronic structure, activity, and spatial arrangement, effectively adjusting the reaction kinetics of the electrochemical process of the catalyst. In this paper, the composition,structure, synthesis of RE alloys and their applications in the field of electrocatalysis are summarized, including the hydrogen evolution reaction, the oxygen evolution reaction, the oxygen reduction reaction, the methanol oxidation reaction, the ethanol oxidation reaction, and other catalytic reactions. At the same time, the present challenges of RE alloy electrocatalytic materials are summarized and their future development direction is pointed out. In the field of electrocatalysis, the cost of catalyst is too high and the stability is not strong. Therefore, the testing process should be related to the actual application, and the test method should be standardized, so as to carry forward the field of electrocatalysis.展开更多
To search the new effective nitrogen reduction reaction(NRR)electrocatalyst is very important for the ammonia-based industry.Herein,we reported the design of a novel NRR electrocatalyst with Ru NPs loaded on oxygen-va...To search the new effective nitrogen reduction reaction(NRR)electrocatalyst is very important for the ammonia-based industry.Herein,we reported the design of a novel NRR electrocatalyst with Ru NPs loaded on oxygen-vacancy TiO2(Ru/TiO2-Vo).Structural characterizations revealed that oxygen vacancy was loaded in the matrix of Ru/TiO2-Vo.Electrocatalytic results indicated that Ru/TiO2-Vo showed good NRR performance(2.11μg h^-1 cm^-2).Contrast tests showed that NRR property of Ru/TiO2-Vo was much better than those of Ru/TiO-12(B)(0.53μg hcm^-2)and Ru/P25(0.42μg h^-1 cm^-2).Furthermore,density functional theory calculation results indicated catalytic mechanism of NRR and rate-determining step(*N2+1/2 H2→*N+*NH)was the potential-determining step with the overpotential requirement of 0.21 V.A combination of electronic structure analysis and catalytic measurement shed light on the synergistic effect of Ru and oxygen vacancy on the NRR performance.展开更多
A series of triple hierarchical micro-mesomacroporous N-doped carbon shells with hollow cores have been successfully prepared via etching N-doped hollow carbon spheres with CO_2 at high temperatures.The surface areas,...A series of triple hierarchical micro-mesomacroporous N-doped carbon shells with hollow cores have been successfully prepared via etching N-doped hollow carbon spheres with CO_2 at high temperatures.The surface areas, total pore volumes and microporepercentages of the CO_2-activated samples evidently increase with increasing activation temperature from 800 to950 °C, while the N contents show a contrary trend from7.6 to 3.8 at%. The pyridinic and graphitic nitrogen groups are dominant among various N-containing groups in the samples. The 950 °C-activated sample(CANHCS-950) has the largest surface area(2072 m^2 g^(-1)), pore volume(1.96 cm^3 g^(-1)), hierarchical micro-mesopore distributions(1.2, 2.6 and 6.2 nm), hollow macropore cores(*91 nm)and highest relative content of pyridinic and graphitic N groups. This triple micro-meso-macropore system could synergistically enhance the activity because macropores could store up the reactant, mesopores could reduce the transport resistance of the reactants to the active sites, and micropores could be in favor of the accumulation of ions.Therefore, the CANHCS-950 with optimized structure shows the optimal and comparable oxygen reduction reaction(ORR) activity but superior methanol tolerance and long-term durability to commercial Pt/C with a 4 e--dominant transfer pathway in alkaline media. These excellent properties in combination with good stability and recyclability make CANHCSs among the most promising metal-free ORR electrocatalysts reported so far in practical applications.展开更多
The main difficulty in the extensive commercial use of polymer electrolyte membrane fuel cells (PEMFCs) is the use of noble metals such as Pt-based electrocatalyst at the cathode, which is essential to ease the oxyg...The main difficulty in the extensive commercial use of polymer electrolyte membrane fuel cells (PEMFCs) is the use of noble metals such as Pt-based electrocatalyst at the cathode, which is essential to ease the oxygen reduction reaction (ORR) in fuel cells (FCs). To eliminate the high loading of Pt-based electrocatalysts to minimize the cost, extensive study has been carried out over the previous decades on the non-noble metal catalysts. Development in enhancing the ORR performance of FCs is mainly due to the doped carbon materials, Fe and Co-based electrocatalysts, these materials could be considered as probable substitutes for Pt-based catalysts. But the stability of these non-noble metal electrocatalysts is low and the durability of these metals remains unclear. The three basic reasons of instability are: (i) oxidative occurrence by H2O2, (ii) leakage of the metal site and (iii) protonation by probable anion adsorption of the active site. Whereas leakage of the metal site has been almost solved, more work is required to understand and avoid losses from oxidative attack and protonation. The ORR performance such as stability tests are usually run at low current densities and the lifetime is much shorter than desired need. Therefore, improvement in the ORR activity and stability afe the key issues of the non-noble metal electrocatalyst. Based on the consequences obtained in this area, numerous future research directions are projected and discussed in this paper. Hence, this review is focused on improvement of stability and durability of the non-noble metal electrocatalyst.展开更多
Developing low-cost and highly-efficient electrocatalysts for renewable energy conversion technologies has attracted even-increasing attention. Molybdenum carbide materials have recently emerged as a type of promising...Developing low-cost and highly-efficient electrocatalysts for renewable energy conversion technologies has attracted even-increasing attention. Molybdenum carbide materials have recently emerged as a type of promising catalysts for electrocatalytic reactions due to the earth-abundance and Pt-resembled electrical properties. In this work, taking the advantage of the interaction between the basic groups of the Mo(VI)-melamine polymer and the acidic groups on the surface of the oxidized carbon nanotubes(CNTs), N-doped CNTs supported Mo2C nanoparticles(Mo2C/NCNT) are prepared, which exhibit outstanding electrocatalytic activity and durability for both the hydrogen evolution and oxygen reduction reactions. The impressive performance of Mo2C/NCNT can be attributed to the small size of Mo2C particles, the large exposure ratio of surface sites and the presence of N-doped CNTs. This work enlarges the multi-field applications of molybdenum carbide-base materials as promising non-precious metal electrocatalysts, which is of great significance for sustainable energy-related technologies.展开更多
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financially supported by the National Natural Science Foundation of China(21674068,52173133,52161145402)the Sichuan Science and Technology Department(2021YFH0180)。
文摘Covalent organic frameworks(COFs)have emerged as a class of promising supports for electrocatalysis because of their advantages including good crystallinity,highly ordered pores,and structural diversity.However,their poor conductivity represents the main obstruction to their practical application.Here,we reported a novel synthesis strategy for synergistically endowing a triphenylamine-based COFs with improved electrical conductivity and excellent catalytic activity for oxygen reduction,via the in-situ redox deposition and confined growth of palladium nanoparticles inside the porous structure of COFs using reductive triphenylamine frameworks as reducing agent;meanwhile,the triphenylamine unit was oxidized to radical cation structure and affords radical cation COFs with conductivity as high as3.2*10^(-1) S m^(-1).Such a uniform confine palladium nanoparticle on highly conductive COFs makes it an efficient electrocatalyst for four-electron oxygen reduction reaction(4e-ORR),showing excellent activities and fast kinetics with a remarkable half-wave potential(E_(1/2))of 0.865 V and an ultralow Tafel slope of 39.7 mV dec^(-1) in alkaline media even in the absence of extra commercial conductive fillers.The generality of this strategy was proved by preparing the different metal and metal alloy nanoparticles supported on COFs(Au@COF,Pt@COF,AuPd@COF,AgPd@COF,and PtPd@COF)using reductive triphenylamine frameworks as reducing agent.This work not only provides a facile strategy for the fabrication of highly conductive COF supported ORR electrocatalysts,but also sheds new light on the practical application of Zn-air battery.
基金the support from the National Natural Science Foundation of China(21773146,22171176 and 22102092)the Fok Ying-Tong Education Foundation for Outstanding Young Teachers in University+2 种基金the Research Funds of Shaanxi Normal Universitythe Fundamental Research Funds for the Central Universitiesthe NRF of Korea(NRF-2021R1A3B1076539 and NRF-2020R1I1A1A01074630)。
文摘Electrocatalytic oxygen reduction and evolution reactions are involved in new energy conversion and storage technologies,such as various fuel cells and metal-air batteries and also water splitting devices[1,2].However,both reactions are very slow in kinetics,and thus catalysts are required[3,4].
基金supported by the National Natural Science Foundation of China(21838003,91834301 and 21978278)the Shanghai Scientific and Technological Innovation Project(18JC1410500 and 19JC1410400)the Fundamental Research Funds for the Central Universities(222201718002).
文摘Defect-engineered carbon materials have been emerged as promising electrocatalysts for oxygen reduction reaction(ORR)in metal-air batteries.Developing a facile strategy for the preparation of highly active nanocarbon electrocatalysts remains challenging.Herein,a low-cost and simple route is developed to synthesize defective graphene by pyrolyzing the mixture of glucose and carbon nitride.Molecular dynamics simulations reveal that the graphene formation is ascribed to two-dimensional layered feature of carbon nitride,and high compatibility of carbon nitride/glucose systems.Structural measurements suggest that the graphene possesses rich edge and topological defects.The graphene catalyst exhibits higher power density than commercial Pt/C catalyst in a primary Zn-air battery.Combining experimental results and theoretical thermodynamic analysis,it is identified that graphitic nitrogen-modified topological defects at carbon framework edges are responsible for the decent ORR performance.The strategy presented in this work can be can be scaled up readily to fabricate defective carbon materials.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIP)(NRF,2021R1C1C1013953,2022K1A4A7A04094394,2022K1A4A7A04095890)。
文摘The electrochemical reduction of carbon dioxide offers a sound and economically viable technology for the electrification and decarbonization of the chemical and fuel industries.In this technology,an electrocatalytic material and renewable energy-generated electricity drive the conversion of carbon dioxide into high-value chemicals and carbon-neutral fuels.Over the past few years,single-atom catalysts have been intensively studied as they could provide near-unity atom utilization and unique catalytic performance.Single-atom catalysts have become one of the state-of-the-art catalyst materials for the electrochemical reduction of carbon dioxide into carbon monoxide.However,it remains a challenge for single-atom catalysts to facilitate the efficient conversion of carbon dioxide into products beyond carbon monoxide.In this review,we summarize and present important findings and critical insights from studies on the electrochemical carbon dioxide reduction reaction into hydrocarbons and oxygenates using single-atom catalysts.It is hoped that this review gives a thorough recapitulation and analysis of the science behind the catalysis of carbon dioxide into more reduced products through singleatom catalysts so that it can be a guide for future research and development on catalysts with industry-ready performance for the electrochemical reduction of carbon dioxide into high-value chemicals and carbon-neutral fuels.
基金Natural Science Foundation of Jiangsu Province (BK20210735)National Natural Science Foundation of China (52201269, 52302296)+4 种基金Collaborative Innovation Center of Suzhou Nano Science and Technologythe 111 Projectthe Suzhou Key Laboratory of Functional Nano and Soft MaterialsJiangsu Key Laboratory for Carbon-Based Functional Materials & Devicesthe funding from the Gusu leading talent plan for scientific and technological innovation and entrepreneurship (ZXL2022487)。
文摘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.
基金supported by the Natural Science Foundation of Anhui Province(No.2208085J01 and No.2208085QA28).
文摘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.
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financially supported by the National Natural Science Foundation of China (U2032157)the Natural Science Foundation of Jiangsu Province (BK20201425)。
文摘The growth of electrochemically inert segregation layers on the surface of solid oxide fuel cell cathodes has become a bottleneck restricting the development of perovskite-structured oxygen reduction catalysts.Here,we report a new discovery in which enriched Ba and Fe ions on the near-surface of Nd_(1/2)Ba_(1/2)Co_(1/3)Fe_(1/3)Mn_(1/3)O_(3-δ)spontaneously agglomerate into dispersed Ba_(5)Fe_(2)O_(8) nanoparticles and maintain a highly active and durable perovskite structure on the surface.This unique surface selfcleaning phenomenon is related to the low average potential energy of Ba_(5)Fe_(2)O_(8),which is grown on the near-surface layer.The electrochemically inert Ba_(5)Fe_(2)O_(8) segregation layer on the near-surface of the perovskite catalyst achieves self-cleaning by regulating the formation energy of enriched metal oxides.This self-cleaned perovskite surface exhibits an ultrafast oxygen exchange rate,high catalytic activity for the oxygen reduction reaction,and good adaptability to the actual working conditions of solid oxide fuel cell stacks.This study paves a new way for overcoming the stubborn problem of perovskite catalyst surface deactivation and enriches the scientific knowledge of surface catalysis.
基金funded by National Natural Science Foundation of China (21975129)Natural Science Foundation of Jiangsu Province (BK20190759)+1 种基金Nanjing Forestry UniversityPostgraduate Research & Practice Innovation Program of Jiangsu Province (SJCX21_0337)。
文摘Developing high efficient Pd-based electrocatalysts for oxygen reduction reaction(ORR) is still challenging for alkaline membrane fuel cell,since the strong oxygen adsorption energy and easy agglomerative intrinsic properties. In order to simultaneously solve these problems, Pd/Co_(3)O_(4)–N–C multidimensional materials with porous structures is designed as the ORR catalysts. In details, the ZIF-67 with polyhedral structure was firstly synthesized and then annealed at high-temperature to prepare the N-doped Co_(3)O_(4)carbon-based material, which was used to homogeneously confine Pd nanoparticles and obtained the Pd/Co_(3)O_(4)–N–C series catalysts. The formation of Co–N and C–N bond could provide efficient active sites for ORR. Simultaneously, the strong electronic interaction in the interface between the Pd and N-doped Co_(3)O_(4)could disperse and avoid the agglomeration of Pd nanoparticles and ensure the exposure of active sites, which is crucial to lower the energy barrier toward ORR and substantially enhance the ORR kinetics. Hence, the Pd/Co_(3)O_(4)–N–C nanocompounds exhibited excellent ORR catalytic performance, ideal Pd mass activity, and durability in 0.1 mol L-1KOH solution compared with Co_(3)O_(4)–N–C and Pd/C. The scalable synthesis method, relatively low cost, and excellent electrochemical ORR performance indicated that the obtained Pd/Co_(3)O_(4)–N–C electrocatalyst had the potential for application on fuel cells.
基金supported by the National Key Research and Development Program of China(No.2022YFE0110400)the National Natural Science Foundation of China(Nos.52122207,52173245,52130206,U20A20337,and 52221006)the Fundamental Research Funds for the Central Universities(No.CLYY2022).
文摘Ruthenium(Ru)is an attractive potential alternative to platinum as an electrocatalyst for the oxygen reduction reaction(ORR),in virtue of its high catalytic selectivity and relatively low price.In this work,a series of well-dispersed nitrogen-coordinated Ru-clusters on carbon black(Ru_(x)N_(y)/C)were prepared by pyrolyzing different Ru-containing sandwich compounds as the Ru sources.The higher thermal stability of these complexed sandwich precursors(bis(1,2,3,4,5-pentamethylcyclopentadienyl)Ru(II)monomer,dichloro(p-cymene)Ru(II)dimer,and chloro(1,2,3,4,5-pentamethylcyclopentadienyl)Ru(II)tetramer)affords the control of coordinated state for the resulting Ru-clusters,in comparison of that derived from ruthenium chlorides.After the pyrolysis treatment,the Ru coordinated state in Ru_(x)N_(y)/C,with the Ru–N and Ru–Ru bonds,still showed the structural inheritance from the Ru(II)monomer,dimer,and tetramer,but using ruthenium chlorides as the Ru source resulted in the nanoscale Ru agglomerations.The ORR testing exhibited that the Ru_(x)N_(y)/C sample derived from the Ru(II)tetramer(Ru_(x)N_(y)/C-T)presents the higher catalytic activity than the other obtained samples in either alkaline or acidic electrolytes.Even in the acidic electrolyte,Ru_(x)N_(y)/C-T shows the comparable ORR activity to that of Pt/C catalysts,and it shows the superior tolerance against methanol and CO.The X-ray absorption spectroscopy and density functional theory calculations demonstrate that these tetra-nuclear Ru-clusters could be the most active site due to their broadened d-orbital bands and lower energy d-band center than those of other subnano species and nanocrystals,and their favorable Yeager-type adsorption of O_(2)-molecules is also contributed to promoting O–O bond cleavage and accelerating the ORR process.
基金supported by the National Natural Science Foundation of China(Grant No.22272105)the Natural Science Foundation of Shanghai(Grant No.23ZR1423900).
文摘Platinum(Pt)-based materials are still the most efficient and practical catalysts to drive the sluggish kinetics of cathodic oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs).However,their catalysis and stability performance still need to be further improved in terms of corrosion of both carbon support and Pt catalyst particles as well as Pt loading reduction.Based on the developed synthetic strategies of alloying/nanostructuring Pt particles and modifying/innovating supports in developing conventional Pt-based catalysts,Pt single-atom catalysts(Pt SACs)as the recently burgeoning hot materials with a potential to achieve the maximum utilization of Pt are comprehensively reviewed in this paper.The design thoughts and synthesis of various isolated,alloyed,and nanoparticlecontained Pt SACs are summarized.The single-atomic Pt coordinating with non-metals and alloying with metals as well as the metal-support interactions of Pt single-atoms with carbon/non-carbon supports are emphasized in terms of the ORR activity and stability of the catalysts.To advance further research and development of Pt SACs for viable implementation in PEMFCs,various technical challenges and several potential research directions are outlined.
基金supported by the National Major Research Project(2016YFB0101208)the National Natural Science Foundation of China(21576257)the Natural Science Foundation-Liaoning United Fund(U1508202)~~
文摘Core-shell nanostructures have been widely investigated to improve the electrocatalytic perfor-mance of platinum. However, organic precursors, surfactants or high temperature are usually nec-essary during the preparation procedure. Unfortunately, these requirements limit the application of these methods on a large scale. Herein, a Pdcore@ Pt shell nanostructure was fabricated through the reduction of fcPtCU by dissociated hydrogen at room temperature without the assistance o f either a surfactant or a high-boiling point solvent. The shell thickness of this nanostructure was successfully controlled by varying the amount of fcPtCU; core-shell nanoparticles with a shell thickness of 0.45, 0.75 and 0.90 nm w ere obtained, as determined by TEM. The remarkable crystallinity and epitaxial growth of the Pdcore@ Pt shell nanostructure were revealed by HRTEM and EDS. According to ICP and XPS, surface segregation of Pt was established. The impressive ORR performance was attributed to the weak adsorption strength of the OHads species, which resulted from the electron transfer impact between the Pdcore and Ptshell. The facile and clean preparation method can be used to prepare other core-shell nanostructures under a mild atmosphere.
基金Project(10JJ9003) supported by Hunan Provincial Natural Science Foundation and Xiangtan Natural Science United Foundation,China Project(11K023) supported by Scientific Research Fund of Hunan Provincial Education Department,China
文摘Nanoporous Pd and binary Pd-Cu particles were prepared by a hydrothermal method using ethylene glycol as a reduction agent and they were directly immobilized on Ti substrates named as Ti-supported Pd-based catalysts. Their electrocatalytic activity for formic acid oxidation and oxygen reduction reaction (ORR) in alkaline media was examined by voltammetric techniques. Among the as-prepared catalysts, nanoPdslCu19/Ti catalyst presents the highest current density of 39.8 mA/cm2 at -0.5 V or 66.4 mA/cm2 at -0.3 V for formic acid oxidation. The onset potential of ORR on the nanoPdslCU19/Ti catalyst presents an about 70 mV positive shift compared to that on the nanoPd/Ti, and the current density of ORR at -0.3 V is 2.12 mA/cm2, which is 3.7 times larger than that on the nanoPd/Ti.
基金financial support from the National Key R&D Program of China (2022YFB3506200)the National Nature Science Foundation of China (22122113)。
文摘With the rapid development of society and economy, the excessive consumption of fossil energy has led to the global energy and environment crisis. In order to explore the sustainable development of new energy, research based on electrocatalysis has attracted extensive attention in the academic circle. The main challenge in this field is to develop nano-catalysts with excellent electrocatalytic activity and selectivity for target products. The state of the active site in catalyst plays a decisive role in the activity and selectivity of the reaction. In order to design efficient and excellent catalysts, it is an effective means to adjust the electronic structure of catalysts. Electronic effects are also called ligand effects. By alloying with rare earth(RE) elements, electrons can be redistributed between RE elements and transition metal elements, achieving accurate design of the electronic structure of the active site in the alloy. Because of the unique electronic structure of RE, it has been paid attention in the field of catalysis. The outermost shell structure of RE elements is basically the same as that of the lower shell, except that the number of electrons in the 4f orbital is different, but the energy level is similar, so their properties are very similar. When RE elements form compounds, both the f electrons in the outermost shell and the d electrons in the lower outer shell can participate in bonding. In addition, part of the 4f electrons in the third outer shell can also participate in bonding.In order to improve the performance of metal catalysts, alloying provides an effective method to design advanced functional materials. RE alloys can integrate the unique electronic structure and catalytic behavior of RE elements into metal materials, which not only provides an opportunity to adjust the electronic structure and catalytic activity of the active component, but also enhances the structural stability of the alloy and is expected to significantly improve the catalytic performance of the catalyst. From the perspective of electronic and catalytic activity, RE elements have unique electronic configuration and lanthanide shrinkage effect. Alloying with RE elements will make the alloy have more abundant electronic structure, activity, and spatial arrangement, effectively adjusting the reaction kinetics of the electrochemical process of the catalyst. In this paper, the composition,structure, synthesis of RE alloys and their applications in the field of electrocatalysis are summarized, including the hydrogen evolution reaction, the oxygen evolution reaction, the oxygen reduction reaction, the methanol oxidation reaction, the ethanol oxidation reaction, and other catalytic reactions. At the same time, the present challenges of RE alloy electrocatalytic materials are summarized and their future development direction is pointed out. In the field of electrocatalysis, the cost of catalyst is too high and the stability is not strong. Therefore, the testing process should be related to the actual application, and the test method should be standardized, so as to carry forward the field of electrocatalysis.
基金supported by the National Natural Science Foundation of China(Nos.21671172,21625604,21776251,21706229and Z86101001)Zhejiang Provincial Natural Science Foundation(No.LR19B010001)
文摘To search the new effective nitrogen reduction reaction(NRR)electrocatalyst is very important for the ammonia-based industry.Herein,we reported the design of a novel NRR electrocatalyst with Ru NPs loaded on oxygen-vacancy TiO2(Ru/TiO2-Vo).Structural characterizations revealed that oxygen vacancy was loaded in the matrix of Ru/TiO2-Vo.Electrocatalytic results indicated that Ru/TiO2-Vo showed good NRR performance(2.11μg h^-1 cm^-2).Contrast tests showed that NRR property of Ru/TiO2-Vo was much better than those of Ru/TiO-12(B)(0.53μg hcm^-2)and Ru/P25(0.42μg h^-1 cm^-2).Furthermore,density functional theory calculation results indicated catalytic mechanism of NRR and rate-determining step(*N2+1/2 H2→*N+*NH)was the potential-determining step with the overpotential requirement of 0.21 V.A combination of electronic structure analysis and catalytic measurement shed light on the synergistic effect of Ru and oxygen vacancy on the NRR performance.
基金the financial support from the National Key Research and Development Program of China(2016YFB0700204)NSFC(51502327,51602332)+1 种基金Science and Technology Commission of Shanghai Municipality(15520720400,15YF1413800,14DZ2261203 and 16DZ2260603)Key Project for Young Researcher of State Key Laboratory of High Performance Ceramics and Superfine Microstructure and One Hundred Talent Plan of Chinese Academy of Sciences
文摘A series of triple hierarchical micro-mesomacroporous N-doped carbon shells with hollow cores have been successfully prepared via etching N-doped hollow carbon spheres with CO_2 at high temperatures.The surface areas, total pore volumes and microporepercentages of the CO_2-activated samples evidently increase with increasing activation temperature from 800 to950 °C, while the N contents show a contrary trend from7.6 to 3.8 at%. The pyridinic and graphitic nitrogen groups are dominant among various N-containing groups in the samples. The 950 °C-activated sample(CANHCS-950) has the largest surface area(2072 m^2 g^(-1)), pore volume(1.96 cm^3 g^(-1)), hierarchical micro-mesopore distributions(1.2, 2.6 and 6.2 nm), hollow macropore cores(*91 nm)and highest relative content of pyridinic and graphitic N groups. This triple micro-meso-macropore system could synergistically enhance the activity because macropores could store up the reactant, mesopores could reduce the transport resistance of the reactants to the active sites, and micropores could be in favor of the accumulation of ions.Therefore, the CANHCS-950 with optimized structure shows the optimal and comparable oxygen reduction reaction(ORR) activity but superior methanol tolerance and long-term durability to commercial Pt/C with a 4 e--dominant transfer pathway in alkaline media. These excellent properties in combination with good stability and recyclability make CANHCSs among the most promising metal-free ORR electrocatalysts reported so far in practical applications.
基金supported by the National Natural Science Foundation of China(21306119)the Key Research and Development Projects in Sichuan Province(2017GZ0397,2017CC0017)+1 种基金the Science and Technology Project of Chengdu(2015-HM01-00531-SF)the Outstanding Young Scientist Foundation of Sichuan University(2013SCU04A23)
文摘The main difficulty in the extensive commercial use of polymer electrolyte membrane fuel cells (PEMFCs) is the use of noble metals such as Pt-based electrocatalyst at the cathode, which is essential to ease the oxygen reduction reaction (ORR) in fuel cells (FCs). To eliminate the high loading of Pt-based electrocatalysts to minimize the cost, extensive study has been carried out over the previous decades on the non-noble metal catalysts. Development in enhancing the ORR performance of FCs is mainly due to the doped carbon materials, Fe and Co-based electrocatalysts, these materials could be considered as probable substitutes for Pt-based catalysts. But the stability of these non-noble metal electrocatalysts is low and the durability of these metals remains unclear. The three basic reasons of instability are: (i) oxidative occurrence by H2O2, (ii) leakage of the metal site and (iii) protonation by probable anion adsorption of the active site. Whereas leakage of the metal site has been almost solved, more work is required to understand and avoid losses from oxidative attack and protonation. The ORR performance such as stability tests are usually run at low current densities and the lifetime is much shorter than desired need. Therefore, improvement in the ORR activity and stability afe the key issues of the non-noble metal electrocatalyst. Based on the consequences obtained in this area, numerous future research directions are projected and discussed in this paper. Hence, this review is focused on improvement of stability and durability of the non-noble metal electrocatalyst.
基金supported by the National Natural Science Foundation of China(21421001 , 21573115)the 111 project (B12015)+1 种基金the Fundamental Research Funds for the Central Universities(63185015)the Foundation of State Key Laboratory of Highefficiency Utilization of Coal and Green Chemical Engineering (2017-K13)
文摘Developing low-cost and highly-efficient electrocatalysts for renewable energy conversion technologies has attracted even-increasing attention. Molybdenum carbide materials have recently emerged as a type of promising catalysts for electrocatalytic reactions due to the earth-abundance and Pt-resembled electrical properties. In this work, taking the advantage of the interaction between the basic groups of the Mo(VI)-melamine polymer and the acidic groups on the surface of the oxidized carbon nanotubes(CNTs), N-doped CNTs supported Mo2C nanoparticles(Mo2C/NCNT) are prepared, which exhibit outstanding electrocatalytic activity and durability for both the hydrogen evolution and oxygen reduction reactions. The impressive performance of Mo2C/NCNT can be attributed to the small size of Mo2C particles, the large exposure ratio of surface sites and the presence of N-doped CNTs. This work enlarges the multi-field applications of molybdenum carbide-base materials as promising non-precious metal electrocatalysts, which is of great significance for sustainable energy-related technologies.