The structural modulation of metal-based heterostructure plays a vital role in achieving enhanced performances for highly efficient electrocatalysis.Here we design submonolayered Ru-modified Pd mesoporous nanosheets(P...The structural modulation of metal-based heterostructure plays a vital role in achieving enhanced performances for highly efficient electrocatalysis.Here we design submonolayered Ru-modified Pd mesoporous nanosheets(Pd-Ru MNSs)with the exposure of both Pd and Ru active sites as well as the high atomic utilization of two-dimensional structure.The obtained Pd-Ru MNSs can act as a highly efficient multifunctional catalyst for hydrogen evolution reaction(HER)and alcohol oxidation reactions including ethylene glycol oxidation(EGOR)and ethanol oxidation(EOR),offering new opportunities towards the alcohol oxidation assisted hydrogen production.Specifically,Pd-Ru MNSs demonstrate excellent HER performance in alkaline electrolyte,requiring an overpotential of only 16mV to reach 10mAcm^(−2),significantly outperforming Pd mesoporous nanosheets and commercial catalysts.Density functional theory calculations reveal that the Ru sites in Pd-Ru MNSs could facilitate the water adsorption,accelerate the water dissociation,and optimize the hydrogen desorption,leading to the superior HER activity.Pd-Ru MNSs also exhibit high mass activities of 11.19 A mg^(−1)Pd for EGOR and 8.84 A mg^(−1)Pd for EOR,which is 7.8 and 9.6 times than that of commercial Pd/C,respectively.The EGOR reaction pathway over Pd-Ru MNSs was further investigated by using in situ Fourier-transform infrared spectroscopy.展开更多
Pt based materials are the most efficient electrocatalysts for the oxygen reduction reaction(ORR)and methanol oxidation reaction(MOR)in fuel cells.Maximizing the utilization of Pt based materials by modulating their m...Pt based materials are the most efficient electrocatalysts for the oxygen reduction reaction(ORR)and methanol oxidation reaction(MOR)in fuel cells.Maximizing the utilization of Pt based materials by modulating their morphologies to expose more active sites is a fundamental objective for the practical application of fuel cells.Herein,we report a new class of hierarchically skeletal Pt-Ni nanocrystals(HSNs)with a multi-layered structure,prepared by an inorganic acid-induced solvothermal method.The addition of H_(2)SO_(4)to the synthetic protocol provides a critical trigger for the successful growth of Pt-Ni nanocrystals with the desired structure.The Pt-Ni HSNs synthesized by this method exhibit enhanced mass activity of 1.25 A mgpt−1 at 0.9 V(versus the reversible hydrogen electrode)towards ORR in 0.1-M HClO_(4),which is superior to that of Pt-Ni multi-branched nanocrystals obtained by the same method in the absence of inorganic acid;it is additionally 8.9-fold higher than that of the commercial Pt/C catalyst.Meanwhile,it displays enhanced stability,with only 21.6%mass activity loss after 10,000 cycles(0.6–1.0 V)for ORR.Furthermore,the Pt-Ni HSNs show enhanced activity and anti-toxic ability in CO for MOR.The superb activity of the Pt-Ni HSNs for ORR and MOR is fully attributed to an extensively exposed electrochemical surface area and high intrinsic activity,induced by strain effects,provided by the unique hierarchically skeletal alloy structure.The novel open and hierarchical structure of Pt-Ni alloy provides a promising approach for significant improvements of the activity of Pt based alloy electrocatalysts.展开更多
Two-dimensional(2D)MXene and single-atom(SA)catalysts are two frontier research fields in catalysis.2D materials with unique geometric and electronic structures can modulate the catalytic performance of supported SAs,...Two-dimensional(2D)MXene and single-atom(SA)catalysts are two frontier research fields in catalysis.2D materials with unique geometric and electronic structures can modulate the catalytic performance of supported SAs,which,in turn,affect the intrinsic activity of 2D materials.Density functional theory calculations were used to systematically explore the potential of O-terminated V2C MXene(V_(2)CO_(2))-supported transition metal(TM)SAs,including a series of 3d,4d,and 5d metals,as oxygen reduction reaction(ORR)and hydrogen oxidation reaction(HOR)catalysts.The combination of TM SAs and V_(2)CO_(2)changes their electronic structure and enriches the active sites,and consequently regulates the intermediate adsorption energy and catalytic activity for ORR and HOR.Among the investigated TM-V_(2)CO_(2)models,Sc-,Mn-,Rh-,and PtMCCh showed high ORR activity,while Sc-,Ti-,V-,Cr-,and Mn-V_(2)CO_(2)exhibited high HOR activity.Specifically,Mn-and Sc-V_(2)CO_(2)are expected to serve as highly efficient and cost-effective bifunctional catalysts for fuel cells because of their high catalytic activity and stability.This work provides theoretical guidance for the rational design of efficient ORR and HOR bifunctional catalysts.展开更多
The oxidative upgrading of organic compounds is essential for synthesizing value-added chemicals that support various industries,including pharmaceuticals,agrochemicals,and materials science.Aerobic oxidation,using mo...The oxidative upgrading of organic compounds is essential for synthesizing value-added chemicals that support various industries,including pharmaceuticals,agrochemicals,and materials science.Aerobic oxidation,using molecular O_(2)(or air)as a green oxidant,offers a more sustainable alternative to traditional oxidation methods that rely on hazardous or strong toxic oxidants.However,conventional thermal aerobic oxidation processes typically require high temperatures,resulting in a significant carbon footprint.In contrast,using green energy sources(e.g.,solar energy and electricity)as driving forces provides a more environmentally friendly approach for aerobic oxidation reactions.In this mini review,we summarize innovative approaches to aerobic oxidation reactions for upgrading organic compounds,including photocatalytic,electrochemical,and photoelectrochemical processes.For each approach,we place particular emphasis on the key design principle,representative oxidation reactions,reaction mechanisms,and notable achievements.Additionally,we discuss the challenges and prospects for promoting these emerging technologies,highlighting their potential to drive advancements toward sustainability in organic oxidation reactions.展开更多
Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electro...Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electrocatalytic oxidations of saturated alcohols(C_(1)-C_(6))to selectively form formate using Ni Co hydroxide(Ni Co-OH)derived Ni Co_(2)O_(4)solid-acid electrocatalysts with balanced Lewis acid(LASs)and Brønsted acid sites(BASs).Thermal treatment transforms BASs-rich(89.6%)Ni Co-OH into Ni Co_(2)O_(4)with nearly equal distribution of LASs(53.1%)and BASs(46.9%)which synergistically promote adsorption and activation of OH-and alcohol molecules for enhanced oxidation activity.In contrast,BASs-enriched Ni Co-OH facilitates formation of higher valence metal sites,beneficial for water oxidation.The combined experimental studies and theoretical calculation imply the oxidation ability of C1-C6alcohols increases as increased number of hydroxyl groups and decreased HOMO-LUMO gaps:methanol(C_(1))<ethylene glycol(C_(2))<glycerol(C3)<meso-erythritol(C4)<xylitol(C5)<sorbitol(C6),while the formate selectivity shows the opposite trend from 100 to 80%.This study unveils synergistic roles of LASs and BASs,as well as hydroxyl group effect in electro-upgrading of alcohols using solid-acid electrocatalysts.展开更多
Cytochrome P450 enzymes (P450s) belong to a large family of oxidative hemeproteins and catalyze highly diverse oxygenation reactions that are involved in the biosynthesis of various natural products. Here, we report a...Cytochrome P450 enzymes (P450s) belong to a large family of oxidative hemeproteins and catalyze highly diverse oxygenation reactions that are involved in the biosynthesis of various natural products. Here, we report a multifunctional cytochrome P450 enzyme, PyrE2, which catalyzes the regioselective, successive 6-electron oxidation of an inert methyl group to produce a carboxyl product through formation of the hydroxyl and aldehyde intermediates in pyrroindomycin biosynthesis. The time-course biotransformation was characterized by the presence of the hydroxyl and aldehyde intermediates, the lag of the formation of the carboxyl product, and the subsequent loss of both intermediates, indicating that each 2-electron oxidation exhibits the distributive mechanism that requires substrate binding and product releasing. Bioinformatics analysis shows that the homologs of pyrE2 are common in the gene clusters of the spirotetronates varying in the oxidative state of the corresponding exocyclic carbon, indicating the generality and diversity of P450-catalyzed oxygenation in related biosynthetic pathways.展开更多
metal oxide electronic interactions in composite electrocatalysts have a considerable impact on their catalytic capability.In this study,we successfully synthesized an electrocatalytic material composed of MoO_(3)/C s...metal oxide electronic interactions in composite electrocatalysts have a considerable impact on their catalytic capability.In this study,we successfully synthesized an electrocatalytic material composed of MoO_(3)/C speciessupported Pd nanoparticles(Pd-MoO_(3)/C)using a convenient hydrothermal method,which exhibited excellent catalytic activities for both ethanol oxidation and oxygen reduction in KOH media.The specific activity of PdMoO_(3)/C toward ethanol oxidation with MoO_(3)loading(40wt%)was~2.6 times greater than that for the commercial Pd/C(10 wt%)with the same Pd content.In particular,the activity could effectively hold up to~60%of its maximum activity after 500-cycle tests,demonstrating improved cyclical stability.Notably,the fast electron transfer kinetics toward oxygen reduction for Pd-MoO_(3)/C(40%)were also comparable to those of commercial Pt/C(20 wt%)catalysts.These superior electrochemical features are primarily derived from the stronger electronic coupling between Pd and MoO_(3)through charge transfer,which can supply more active centers and improve the anti-poisoning ability.Meanwhile,the MoO_(3)species in the Pd-MoO_(3)/C composite may provide additional benefits in terms of electrical conductivity and dispersion.展开更多
To achieve the goals of the peak carbon dioxide emissions and carbon neutral,the development and utilization of sustainable clean energy are extremely important.Hydrogen fuel cells are an important system for converti...To achieve the goals of the peak carbon dioxide emissions and carbon neutral,the development and utilization of sustainable clean energy are extremely important.Hydrogen fuel cells are an important system for converting hydrogen energy into electrical energy.However,the slow hydrogen oxidation reaction(HOR)kinetics under alkaline conditions has limited its development.Therefore,elucidating the catalytic mechanism of HOR in acidic and alkaline media is of great significance for the construction of highly active and stable catalysts.In terms of practicality,Pt is still the primary choice for commercialization of fuel cells.On the above basis,we first introduced the hydrogen binding energy theory and bifunctional theory used to describe the HOR activity,as well as the pH dependence.After that,the rational design strategies of Pt-based HOR catalysts were systematically classified and summarized from the perspective of activity descriptors.In addition,we further emphasized the importance of theoretical simulations and in situ characterization in revealing the HOR mechanism,which is crucial for the rational design of catalysts.Moreover,the practical application of Pt-based HOR catalysts in fuel cells was also presented.In closing,the current challenges and future development directions of HOR catalysts were discussed.This review will provide a deep understanding for exploring the mechanism of highly efficient HOR catalysts and the development of fuel cells.展开更多
Efficient,robust and cost-effective electrocatalysts that catalyze hydrogen evolution/oxidation reaction(HER/HOR)in alkaline media are highly demanded.Recently,single-atom catalysts(SACs)have emerged as new promising ...Efficient,robust and cost-effective electrocatalysts that catalyze hydrogen evolution/oxidation reaction(HER/HOR)in alkaline media are highly demanded.Recently,single-atom catalysts(SACs)have emerged as new promising candidates;however,the rational design of supports and the optimization of coordination environment between supports and metal atoms are challenging.In this work,we successfully fabricate atomically dispersed ruthenium(Ru)species,which are strongly coordinated by N and S dual heteroatoms on holey graphene(RuSA/NSG),as an excellent bifunctional catalyst for HER/HOR.In alkaline media,the developed catalyst exhibits high catalytic performance with a low overpotential of 57.3 mV to drive a current density of 10 mA cm^(-1) for HER,and its mass activity is about 5.8 times higher than that of commercial Pt/C and Ru/C catalysts at an overpotential of 100 mV.Similarly,considerable HOR performance of Ru SA/NSG is verified to be superior to Pt/C and Ru/C.Furthermore,X-ray-based spectroscopy measurements and density-functional theory calculations have confirmed that,compared with Ru–N_(4),the tailored Ru–N_(4)–S_(2) with nearby S dopants can act as more active centers to greatly accelerate the sluggish HER/HOR kinetics in alkaline media.The present work provides a new atomic-level engineering strategy to modulate catalytic activities of SACs via the coordination design using dual heteroatoms on the carbon support.展开更多
Studies have extensively addressed the development of electrocatalytic technologies for energy storage and conversion,fuel production,and environmental protection.Electrode processes such as different oxidation and re...Studies have extensively addressed the development of electrocatalytic technologies for energy storage and conversion,fuel production,and environmental protection.Electrode processes such as different oxidation and reduction reactions play a vital and significant role in these technologies.In this regard,efficient,inexpensive,and stable electrocatalysts capable can significantly promote electrochemical reactions.Unique features of metal–organic frameworks(MOFs)such as their high porosity,tunable structure,size,and pore shape,high surface area,and redox properties have introduced them as an ideal electrocatalyst candidate.This review is thus aimed at elucidating the role of MOF-based materials(pristine,derivatives and composites)as efficient electrocatalysts in energy and sensing-related oxidation and reduction reactions such as oxygen reduction reaction(ORR),hydrogen oxidation reaction(HOR),carbon dioxide reduction reaction(CO_(2)RR),urea oxidation reaction(UOR),alcohol oxidation reaction(AOR),nitrogen reduction reaction(NRR),and glucose oxidation reaction(GOR)in advanced energy and sensing devices.Also,the structure–property relationship of the electrocatalyst was elaborated for each electrocatalytic reaction.Finally,perspectives on the potential research topics for practical use of MOF-based electrocatalysts are addressed.The present review can improve the interest in MOF-based electrocatalysts to study different oxidation and reduction reactions in energy and sensing systems.展开更多
Establishing an energy-saving and affordable hydrogen production route from infinite seawater presents a promising strategy for achieving carbon neutrality and low-carbon development.Compared with the kinetically slug...Establishing an energy-saving and affordable hydrogen production route from infinite seawater presents a promising strategy for achieving carbon neutrality and low-carbon development.Compared with the kinetically sluggish oxygen evolution reaction(OER),the thermodynamically advantageous sulfion oxidation reaction(SOR)enables the S^(2-)pollutants recovery while reducing the energy input of water electrolysis.Here,a nanoporous NiMo alloy ligament(np-NiMo)with AlNi_(3)/Al_(5)Mo heterostructure was prepared for hydrogen evolution reaction(HER,-0.134V versus reversible hydrogen electrode(vs.RHE)at 50mA/cm^(2)),which needs an Al_(89)Ni_(10)Mo_(1)as a precursor and dealloying operation.Further,the np-NiMo alloy was thermal-treated with S powder to generate Mo-doped NiS_(2)(np-NiMo-S)for OER(1.544V vs.RHE at 50mA/cm^(2))and SOR(0.364 V vs.RHE at 50mA/cm^(2)),while still maintaining the nanostructuring advantages.Moreover,for a two-electrode electrolyzer system with np-NiMo cathode(1M KOH+seawater)coupling np-NiMo-S anode(1mol/L KOH+seawater+1 mol/L Na_(2)S),a remarkably ultra-low cell potential of 0.532 V is acquired at 50mA/cm^(2),which is about 1.015 V below that of normal alkaline seawater splitting.The theory calculations confirmed that the AlNi_(3)/Al_(5)Mo heterostructure within np-NiMo promotes H_(2)O dissociation for excellent HER,while the Mo-dopant of np-NiMo-S lowers energy barriers for the rate-determining step from^(*)S_(4)to^(*)S_(8).This work develops two kinds of NiMo alloy with tremendous prominence for achieving energy-efficient hydrogen production from alkaline seawater and sulfur recycling from sulfion-rich sewage.展开更多
Unraveling the essence of electronic structure effected by d-d orbital coupling of transition metal and methanol oxidation reaction(MOR)performance can fundamentally guide high efficient catalyst design.Herein,density...Unraveling the essence of electronic structure effected by d-d orbital coupling of transition metal and methanol oxidation reaction(MOR)performance can fundamentally guide high efficient catalyst design.Herein,density functional theory(DFT)calculations were performed at first to study the d–d orbital interaction of metallic Pt Pd Cu,revealing that the incorporation of Pd and Cu atoms into Pt system can enhance d-d electron interaction via capturing antibonding orbital electrons of Pt to fill the surrounding Pd and Cu atoms.Under the theoretical guidance,Pt Pd Cu medium entropy alloy aerogels(Pt Pd Cu MEAAs)catalysts have been designed and systematically screened for MOR under acid,alkaline and neutral electrolyte.Furthermore,DFT calculation and in-situ fourier transform infrared spectroscopy analysis indicate that Pt Pd Cu MEAAs follow the direct pathway via formate as the reactive intermediate to be directly oxidized to CO_(2).For practical direct methanol fuel cells(DMFCs),the Pt Pd Cu MEAAs-integrated ultra-thin catalyst layer(4–5μm thickness)as anode exhibits higher peak power density of 35 m W/cm^(2) than commercial Pt/C of 20 m W/cm^(2)(~40μm thickness)under the similar noble metal loading and an impressive stability retention at a 50-m A/cm^(2) constant current for 10 h.This work clearly proves that optimizing the intermediate adsorption capacity via d-d orbital coupling is an effective strategy to design highly efficient catalysts for DMFCs.展开更多
Concurrent activation of lattice oxygen(O_L)and molecular oxygen(O_(2))is crucial for the efficient catalytic oxidation of biomass-derived molecules over metal oxides.Herein,we report that the introduction of ultralow...Concurrent activation of lattice oxygen(O_L)and molecular oxygen(O_(2))is crucial for the efficient catalytic oxidation of biomass-derived molecules over metal oxides.Herein,we report that the introduction of ultralow-loading of Ru single atoms(0.42 wt%)into Mn_(2)O_(3)matrix(0.4%Ru-Mn_(2)O_(3))greatly boosts its catalytic activity for the aerobic oxidation of 5-hydroxymethylfurfural(HMF)to 2,5-furandicarboxylic acid(FDCA).The FDCA productivity over the 0.4%Ru-Mn_(2)O_(3)(5.4 mmol_(FDCA)g_(cat)h^(-1))is 4.9 times higher than the Mn_(2)O_(3).Especially,this FDCAproductivity is also significantly higher than that of existing Ru and Mn-based catalysts.Experimental and theoretical investigations discovered that the Ru single atom facilitated the formation of oxygen vacancy(O_(v))in the catalyst,which synergistically weakened the Mn-O bond and promoted the activation of O_L.The co-presence of Ru single atoms and O_(v)also promote the adsorption and activation of both O_(2)and HMF.Consequently,the dehydrogenation reaction energy barrier of the rate-determining step was reduced via both the O_L and chemisorbed O_(2)dehydrogenation pathways,thus boosting the catalytic oxidation reactions.展开更多
Electrochemically induced surface reconstruction offers a novel approach for in situ modulation of the surface structure of nanomaterials.However,comprehensive studies on the surface reconstruction behavior of nanomat...Electrochemically induced surface reconstruction offers a novel approach for in situ modulation of the surface structure of nanomaterials.However,comprehensive studies on the surface reconstruction behavior of nanomaterials under diverse electrochemical operations remain limited.Here,exemplified by three electrochemical operations,including cyclic voltammetry(CV),squarewave potential(SWP)and chronoamperometry(CA),we reveal the structural evolution behavior and the corresponding electrocatalytic activity of bimetallic telluride hollow nanorods(Ir_(1-x)Ru_(x)0Te_(2)HNRs).It was found that the surface Te atoms in Ir_(1-x)Ru_(x)0Te_(2)HNRs undergo preferential leaching during the CV and SWP processes,ultimately leading to the formation of a metal alloy shell.In contrast,during the CA process,the surface reconstruction induced by Te leaching was suppressed by the adsorption of anions on the electrode surface.Electrocatalytic tests show that the CV activated Ir_(0.75)Ru_(0.25)Te_(2)HNRs exhibit excellent activity for the hydrogen oxidation reaction in 0.1 M KOH,with a mass activity of 686 Ag^(-1)at an overpotential of50 mV,which is 2.9 times higher than that of commercialPt/C catalyst.Density functional theory(DFT)computation reveals that the incorporation of Ru optimizes the hydroxyl binding energy of IrRu alloy,thus resulting in the reduced reaction energy barrier of hydrogen oxidation reaction.This work provides a new insight into the design of efficient catalysts through electrochemical surface engineering.展开更多
Highly active and stable electrocatalysts for ethanol oxidation reaction(EOR)are critical for the widespread adoption of direct ethanol fuel cells(DEFCs).However,the low efficiency of C–C bond cleavage of commercial ...Highly active and stable electrocatalysts for ethanol oxidation reaction(EOR)are critical for the widespread adoption of direct ethanol fuel cells(DEFCs).However,the low efficiency of C–C bond cleavage of commercial electrocatalysts not only leads to incomplete ethanol oxidation but also results in the accumulation of poisoning CO species.In this work,silver-platinum hollow nanocubes(AgPt hNCs)are designed and synthesized to achieve high selectivity for the complete 12-electron EOR in an alkaline electrolyte.AgPt h NCs demonstrate a Faradaic efficiency of up to 88.2%at the potential of 0.70 V for the C1 pathway and exhibit a 6.3-fold EOR mass activity than commercial Pt black at the potential of 0.81 V.Moreover,the oxyphilic nature of Ag imparts exceptional long-term stability to AgPt h NCs.Theoretical calculations reveal that the electronic interaction between Pt and Ag effectively modifies the d-band properties of surface Pt atoms,thereby optimizing the adsorption behavior of key intermediates,promoting the dehydrogenation of CH_(3)CO^(*)to CH_(2)CO^(*),and facilitating C–C bond cleavage.The present work provides both theoretical and experimental insights into the utilization of Ag-based alloy catalysts for highperformance DEFCs.展开更多
Interface engineering is a prospective method for improving electrochemical performance,while efficient interfacial tuning is still difficult.Here,a series of WO_(3)-Ir catalysts with tuned interfaces were obtained fr...Interface engineering is a prospective method for improving electrochemical performance,while efficient interfacial tuning is still difficult.Here,a series of WO_(3)-Ir catalysts with tuned interfaces were obtained from WO_(3)support with different surface states.The prepared WO_(3)-O-Ir catalyst with higher interfacial oxygen content shows excellent hydrogen oxidation reaction activity with a mass activity of 54.04 A gIr^(-1)for hydrogen oxidation reaction,which is superior to WO_(3)-W-Ir with higher tungsten content and even commercial Pt/C catalysts.Theoretical calculation and X-ray photoelectron spectroscopy valence band spectrum analyses verify that the position of the d-band center is directly proportional to the interfacial oxygen content.This modulates the electronic structure of the active phase,increasing the binding energy for OH species and enhancing their adsorption capacity,which boost the performance for hydrogen oxidation reaction.展开更多
The development of efficient and robust non-precious metal electrocatalyst to drive the sluggish hydrogen oxidation reaction(HOR)is the key to the practical application of anion exchange membrane fuel cells(AEMFC),whi...The development of efficient and robust non-precious metal electrocatalyst to drive the sluggish hydrogen oxidation reaction(HOR)is the key to the practical application of anion exchange membrane fuel cells(AEMFC),which relies on the rational regulation of intermediates’binding strength.Herein,we reported a simple strategy to manipulate the adsorption energy of OH^(∗)on electrocatalyst surface via engineering Ni/NbO_(x) heterostructures with manageable oxygen vacancy(Ov).Theoretical calculations confirm that the electronic effect between Ni and NbO_(x) could weaken the hydrogen adsorption on Ni,and the interfacial oxygen vacancy tailor hydroxide binding energy(OHBE).The optimized HBE and OHBE contribute to reduce formation energy of water during the alkaline HOR process.Furthermore,in situ Raman spectroscopy monitor the dynamic process that OH^(∗)adsorbed on oxygen vacancy and react with adjacent H^(∗)adsorbed Ni,confirming the vital role of OH^(∗)for alkaline HOR process.As a result,the optimal Ni/NbO_(x) exhibits a remarkable intrinsic activity with a specific activity of 0.036mA/cm^(2),which is 4-fold than that of pristine Ni counterpart and surpasses most non-precious electrocatalysts ever reported.展开更多
Active and poisoning-resistant Ru-based electrocatalysts for the hydrogen oxidation reaction(HOR)are designed and fabricated by integrating Cu/Ru dual single atoms and alloy CuRu nanoparticles(N-(CuRu)_(NP+SA)@NC)thro...Active and poisoning-resistant Ru-based electrocatalysts for the hydrogen oxidation reaction(HOR)are designed and fabricated by integrating Cu/Ru dual single atoms and alloy CuRu nanoparticles(N-(CuRu)_(NP+SA)@NC)through a strategy involving weak chemical reduction and ammonia-assisted gas-phase nitridation.The resultant N-(CuRu)_(NP+SA)@NC electrocatalysts feature nitrogen atoms coordinated to both Cu and Ru metal atoms via strong N-metal interactions.Density functional theory calculations revealed that alloyed CuRu nanoparticles and monodispersed Cu atoms are vital for altering the electronic configuration of the host Ru elements.This finely tuned structure enhanced the adsorption of H and OH and promoted CO oxidation over the N-(CuRu)_(NP+SA)@NC electrocatalyst,resulting in high alkaline HOR activity,as evidenced by the higher exchange current density of 3.74 mA cm^(-2)and high mass activity of 3.28 mAμg_(Ru)^(-1),which are far superior to those of most Ru-based catalysts reported to date.Moreover,the N-(CuRu)_(NP+SA)@NC electrocatalysts are resistant to CO poisoning and can be used at a high concentration of 1000 ppm CO with no distinct decay in the activity,in stark contrast to the commercial Pt/C catalyst under the same conditions.展开更多
Ethylene glycol(EG)is a biomass derivative of polyethylene terephthalate(PET),and its electrocatalytic conversion into high-value chemicals has sparked widespread interest.This study reviews the most recent research d...Ethylene glycol(EG)is a biomass derivative of polyethylene terephthalate(PET),and its electrocatalytic conversion into high-value chemicals has sparked widespread interest.This study reviews the most recent research development in electrocatalysis-based EG to glycolic acid(GA)conversion.Firstly,the strategies and research results of modulating the electronic structure of catalysts for efficient selective GA production from EG are reviewed.Second,by reviewing the data of in-situ Fourier transform infrared spectroscopy and in-situ electrochemically attenuated total reflection surface enhanced infrared absorption spectroscopy,the reaction pathway and catalytic mechanism of EG partial oxidation to GA were clarified.Finally,the design and regulation of catalysts for selective oxidation of EG by electrocatalysis in the future are prospected.展开更多
Storing hydrogen in green methanol is a well-known and cost-effective way for long-term energy storage.However,using green methanol in fuel cell technologies requires electrocatalysts with superior resistance to poiso...Storing hydrogen in green methanol is a well-known and cost-effective way for long-term energy storage.However,using green methanol in fuel cell technologies requires electrocatalysts with superior resistance to poisoning induced by intermediate species.This study introduces a new class of palladium-based rare earth(RE)alloys with exceptional resistance to methanol for the oxygen reduction reaction(ORR)and outstanding resistance to carbon monoxide poisoning for the hydrogen oxidation reaction(HOR).The PdEr catalyst achieved unparalleled ORR activity amongst the Pd-based rare earth alloys and demonstrated remarkable resistance to methanol poisoning,which is two orders of magnitude higher than commercial Pt/C catalysts.Furthermore,the PdEr catalyst shows high hydrogen oxidation activity under 100 ppm CO.Comprehensive analysis demonstrates that the RE element-enriched sublayer tuning of the Pd-skin's surface strain is responsible for the enhanced ORR and HOR capabilities.This modification allows for precise control over the adsorption strength of critical intermediates while concurrently diminishing the adsorption energy of methanol and CO on the PdEr surface.展开更多
基金financial support from the National Natural Science Foundation of China(No.52471219)the Fundamental Research Funds for the Central Universities(No.00007838)+5 种基金financial support from the National Natural Science Foundation of China(No.52471220 and U2441264)the Guangdong Basic and Applied Basic Research Foundation(No.2022A1515140051)financial support from the National Natural Science Foundation of China(No.92163209)Beijing Natural Science Foundation(No.JQ22004)financial support from the National Natural Science Foundation of China(No.52476146)Guangdong Basic and Applied Basic Research Foundation(2023A1515140059,2025A1515011255).
文摘The structural modulation of metal-based heterostructure plays a vital role in achieving enhanced performances for highly efficient electrocatalysis.Here we design submonolayered Ru-modified Pd mesoporous nanosheets(Pd-Ru MNSs)with the exposure of both Pd and Ru active sites as well as the high atomic utilization of two-dimensional structure.The obtained Pd-Ru MNSs can act as a highly efficient multifunctional catalyst for hydrogen evolution reaction(HER)and alcohol oxidation reactions including ethylene glycol oxidation(EGOR)and ethanol oxidation(EOR),offering new opportunities towards the alcohol oxidation assisted hydrogen production.Specifically,Pd-Ru MNSs demonstrate excellent HER performance in alkaline electrolyte,requiring an overpotential of only 16mV to reach 10mAcm^(−2),significantly outperforming Pd mesoporous nanosheets and commercial catalysts.Density functional theory calculations reveal that the Ru sites in Pd-Ru MNSs could facilitate the water adsorption,accelerate the water dissociation,and optimize the hydrogen desorption,leading to the superior HER activity.Pd-Ru MNSs also exhibit high mass activities of 11.19 A mg^(−1)Pd for EGOR and 8.84 A mg^(−1)Pd for EOR,which is 7.8 and 9.6 times than that of commercial Pd/C,respectively.The EGOR reaction pathway over Pd-Ru MNSs was further investigated by using in situ Fourier-transform infrared spectroscopy.
文摘Pt based materials are the most efficient electrocatalysts for the oxygen reduction reaction(ORR)and methanol oxidation reaction(MOR)in fuel cells.Maximizing the utilization of Pt based materials by modulating their morphologies to expose more active sites is a fundamental objective for the practical application of fuel cells.Herein,we report a new class of hierarchically skeletal Pt-Ni nanocrystals(HSNs)with a multi-layered structure,prepared by an inorganic acid-induced solvothermal method.The addition of H_(2)SO_(4)to the synthetic protocol provides a critical trigger for the successful growth of Pt-Ni nanocrystals with the desired structure.The Pt-Ni HSNs synthesized by this method exhibit enhanced mass activity of 1.25 A mgpt−1 at 0.9 V(versus the reversible hydrogen electrode)towards ORR in 0.1-M HClO_(4),which is superior to that of Pt-Ni multi-branched nanocrystals obtained by the same method in the absence of inorganic acid;it is additionally 8.9-fold higher than that of the commercial Pt/C catalyst.Meanwhile,it displays enhanced stability,with only 21.6%mass activity loss after 10,000 cycles(0.6–1.0 V)for ORR.Furthermore,the Pt-Ni HSNs show enhanced activity and anti-toxic ability in CO for MOR.The superb activity of the Pt-Ni HSNs for ORR and MOR is fully attributed to an extensively exposed electrochemical surface area and high intrinsic activity,induced by strain effects,provided by the unique hierarchically skeletal alloy structure.The novel open and hierarchical structure of Pt-Ni alloy provides a promising approach for significant improvements of the activity of Pt based alloy electrocatalysts.
文摘Two-dimensional(2D)MXene and single-atom(SA)catalysts are two frontier research fields in catalysis.2D materials with unique geometric and electronic structures can modulate the catalytic performance of supported SAs,which,in turn,affect the intrinsic activity of 2D materials.Density functional theory calculations were used to systematically explore the potential of O-terminated V2C MXene(V_(2)CO_(2))-supported transition metal(TM)SAs,including a series of 3d,4d,and 5d metals,as oxygen reduction reaction(ORR)and hydrogen oxidation reaction(HOR)catalysts.The combination of TM SAs and V_(2)CO_(2)changes their electronic structure and enriches the active sites,and consequently regulates the intermediate adsorption energy and catalytic activity for ORR and HOR.Among the investigated TM-V_(2)CO_(2)models,Sc-,Mn-,Rh-,and PtMCCh showed high ORR activity,while Sc-,Ti-,V-,Cr-,and Mn-V_(2)CO_(2)exhibited high HOR activity.Specifically,Mn-and Sc-V_(2)CO_(2)are expected to serve as highly efficient and cost-effective bifunctional catalysts for fuel cells because of their high catalytic activity and stability.This work provides theoretical guidance for the rational design of efficient ORR and HOR bifunctional catalysts.
基金support from the National Key R&D Program of China(grant no.2023YFA1507201)the National Natural Science Foundation of China(grant nos.22421005,52120105002,52432006,and 22088102)the Chinese Academy of Sciences(CAS)Project for Young Scientists in Basic Research(grant no.YSBR-004).
文摘The oxidative upgrading of organic compounds is essential for synthesizing value-added chemicals that support various industries,including pharmaceuticals,agrochemicals,and materials science.Aerobic oxidation,using molecular O_(2)(or air)as a green oxidant,offers a more sustainable alternative to traditional oxidation methods that rely on hazardous or strong toxic oxidants.However,conventional thermal aerobic oxidation processes typically require high temperatures,resulting in a significant carbon footprint.In contrast,using green energy sources(e.g.,solar energy and electricity)as driving forces provides a more environmentally friendly approach for aerobic oxidation reactions.In this mini review,we summarize innovative approaches to aerobic oxidation reactions for upgrading organic compounds,including photocatalytic,electrochemical,and photoelectrochemical processes.For each approach,we place particular emphasis on the key design principle,representative oxidation reactions,reaction mechanisms,and notable achievements.Additionally,we discuss the challenges and prospects for promoting these emerging technologies,highlighting their potential to drive advancements toward sustainability in organic oxidation reactions.
基金the financial support from the National Natural Science Foundation of China(52172110,52472231,52311530113)Shanghai"Science and Technology Innovation Action Plan"intergovernmental international science and technology cooperation project(23520710600)+1 种基金Science and Technology Commission of Shanghai Municipality(22DZ1205600)the Central Guidance on Science and Technology Development Fund of Zhejiang Province(2024ZY01011)。
文摘Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electrocatalytic oxidations of saturated alcohols(C_(1)-C_(6))to selectively form formate using Ni Co hydroxide(Ni Co-OH)derived Ni Co_(2)O_(4)solid-acid electrocatalysts with balanced Lewis acid(LASs)and Brønsted acid sites(BASs).Thermal treatment transforms BASs-rich(89.6%)Ni Co-OH into Ni Co_(2)O_(4)with nearly equal distribution of LASs(53.1%)and BASs(46.9%)which synergistically promote adsorption and activation of OH-and alcohol molecules for enhanced oxidation activity.In contrast,BASs-enriched Ni Co-OH facilitates formation of higher valence metal sites,beneficial for water oxidation.The combined experimental studies and theoretical calculation imply the oxidation ability of C1-C6alcohols increases as increased number of hydroxyl groups and decreased HOMO-LUMO gaps:methanol(C_(1))<ethylene glycol(C_(2))<glycerol(C3)<meso-erythritol(C4)<xylitol(C5)<sorbitol(C6),while the formate selectivity shows the opposite trend from 100 to 80%.This study unveils synergistic roles of LASs and BASs,as well as hydroxyl group effect in electro-upgrading of alcohols using solid-acid electrocatalysts.
基金supported in part by grants from the National Key Research and Development Program of China(2022YFC2303100)the National Natural Science Foundation of China(22193070,32030002,81974495 and 21977109)the Innovative Research Team of High-Level Local Universities in Shanghai(SHSMU-ZLCX20212401).
文摘Cytochrome P450 enzymes (P450s) belong to a large family of oxidative hemeproteins and catalyze highly diverse oxygenation reactions that are involved in the biosynthesis of various natural products. Here, we report a multifunctional cytochrome P450 enzyme, PyrE2, which catalyzes the regioselective, successive 6-electron oxidation of an inert methyl group to produce a carboxyl product through formation of the hydroxyl and aldehyde intermediates in pyrroindomycin biosynthesis. The time-course biotransformation was characterized by the presence of the hydroxyl and aldehyde intermediates, the lag of the formation of the carboxyl product, and the subsequent loss of both intermediates, indicating that each 2-electron oxidation exhibits the distributive mechanism that requires substrate binding and product releasing. Bioinformatics analysis shows that the homologs of pyrE2 are common in the gene clusters of the spirotetronates varying in the oxidative state of the corresponding exocyclic carbon, indicating the generality and diversity of P450-catalyzed oxygenation in related biosynthetic pathways.
基金financially supported by the Natural Science Foundation of Shanxi Province(No.201901D111277)the National Natural Science Foundation of China(No.21571119)+1 种基金the Graduate Science and Technology Innovation Project Foundation of Shanxi Normal University(No.2021DCXM71)the Program for New Century Excellent Talents in University(No.NCET-12-1035)。
文摘metal oxide electronic interactions in composite electrocatalysts have a considerable impact on their catalytic capability.In this study,we successfully synthesized an electrocatalytic material composed of MoO_(3)/C speciessupported Pd nanoparticles(Pd-MoO_(3)/C)using a convenient hydrothermal method,which exhibited excellent catalytic activities for both ethanol oxidation and oxygen reduction in KOH media.The specific activity of PdMoO_(3)/C toward ethanol oxidation with MoO_(3)loading(40wt%)was~2.6 times greater than that for the commercial Pd/C(10 wt%)with the same Pd content.In particular,the activity could effectively hold up to~60%of its maximum activity after 500-cycle tests,demonstrating improved cyclical stability.Notably,the fast electron transfer kinetics toward oxygen reduction for Pd-MoO_(3)/C(40%)were also comparable to those of commercial Pt/C(20 wt%)catalysts.These superior electrochemical features are primarily derived from the stronger electronic coupling between Pd and MoO_(3)through charge transfer,which can supply more active centers and improve the anti-poisoning ability.Meanwhile,the MoO_(3)species in the Pd-MoO_(3)/C composite may provide additional benefits in terms of electrical conductivity and dispersion.
基金support of this research by the National Natural Science Foundation of China(Nos.22179034 and 22279030)the Natural Science Foundation of Heilongjiang Province(No.ZD2023B002).
文摘To achieve the goals of the peak carbon dioxide emissions and carbon neutral,the development and utilization of sustainable clean energy are extremely important.Hydrogen fuel cells are an important system for converting hydrogen energy into electrical energy.However,the slow hydrogen oxidation reaction(HOR)kinetics under alkaline conditions has limited its development.Therefore,elucidating the catalytic mechanism of HOR in acidic and alkaline media is of great significance for the construction of highly active and stable catalysts.In terms of practicality,Pt is still the primary choice for commercialization of fuel cells.On the above basis,we first introduced the hydrogen binding energy theory and bifunctional theory used to describe the HOR activity,as well as the pH dependence.After that,the rational design strategies of Pt-based HOR catalysts were systematically classified and summarized from the perspective of activity descriptors.In addition,we further emphasized the importance of theoretical simulations and in situ characterization in revealing the HOR mechanism,which is crucial for the rational design of catalysts.Moreover,the practical application of Pt-based HOR catalysts in fuel cells was also presented.In closing,the current challenges and future development directions of HOR catalysts were discussed.This review will provide a deep understanding for exploring the mechanism of highly efficient HOR catalysts and the development of fuel cells.
基金supported by Center for Computational Science and Engineering at Southern University of Science and Technologyfinancially supported by the National Key Research and Development Program of China (2018YFB1502503)+3 种基金Guangdong Provincial Key Laboratory of Energy Materials for Electric Power (2018B030322001)Shenzhen Key Laboratory Project (ZDSYS201603311013489)Shenzhen Science and Technology Projects for Sustainable Development (KCXFZ202002011010317)the Foundation Research Project of Shenzhen (JCYJ20200109141216566)。
文摘Efficient,robust and cost-effective electrocatalysts that catalyze hydrogen evolution/oxidation reaction(HER/HOR)in alkaline media are highly demanded.Recently,single-atom catalysts(SACs)have emerged as new promising candidates;however,the rational design of supports and the optimization of coordination environment between supports and metal atoms are challenging.In this work,we successfully fabricate atomically dispersed ruthenium(Ru)species,which are strongly coordinated by N and S dual heteroatoms on holey graphene(RuSA/NSG),as an excellent bifunctional catalyst for HER/HOR.In alkaline media,the developed catalyst exhibits high catalytic performance with a low overpotential of 57.3 mV to drive a current density of 10 mA cm^(-1) for HER,and its mass activity is about 5.8 times higher than that of commercial Pt/C and Ru/C catalysts at an overpotential of 100 mV.Similarly,considerable HOR performance of Ru SA/NSG is verified to be superior to Pt/C and Ru/C.Furthermore,X-ray-based spectroscopy measurements and density-functional theory calculations have confirmed that,compared with Ru–N_(4),the tailored Ru–N_(4)–S_(2) with nearby S dopants can act as more active centers to greatly accelerate the sluggish HER/HOR kinetics in alkaline media.The present work provides a new atomic-level engineering strategy to modulate catalytic activities of SACs via the coordination design using dual heteroatoms on the carbon support.
文摘Studies have extensively addressed the development of electrocatalytic technologies for energy storage and conversion,fuel production,and environmental protection.Electrode processes such as different oxidation and reduction reactions play a vital and significant role in these technologies.In this regard,efficient,inexpensive,and stable electrocatalysts capable can significantly promote electrochemical reactions.Unique features of metal–organic frameworks(MOFs)such as their high porosity,tunable structure,size,and pore shape,high surface area,and redox properties have introduced them as an ideal electrocatalyst candidate.This review is thus aimed at elucidating the role of MOF-based materials(pristine,derivatives and composites)as efficient electrocatalysts in energy and sensing-related oxidation and reduction reactions such as oxygen reduction reaction(ORR),hydrogen oxidation reaction(HOR),carbon dioxide reduction reaction(CO_(2)RR),urea oxidation reaction(UOR),alcohol oxidation reaction(AOR),nitrogen reduction reaction(NRR),and glucose oxidation reaction(GOR)in advanced energy and sensing devices.Also,the structure–property relationship of the electrocatalyst was elaborated for each electrocatalytic reaction.Finally,perspectives on the potential research topics for practical use of MOF-based electrocatalysts are addressed.The present review can improve the interest in MOF-based electrocatalysts to study different oxidation and reduction reactions in energy and sensing systems.
基金financially supported by the Guangxi Natural Science Fund for Distinguished Young Scholars(No.2024GXNSFFA010008)the Natural Science Foundation of Jilin Province of China(No.20240101098JC)the National Natural Science Foundation of China(No.22469002)。
文摘Establishing an energy-saving and affordable hydrogen production route from infinite seawater presents a promising strategy for achieving carbon neutrality and low-carbon development.Compared with the kinetically sluggish oxygen evolution reaction(OER),the thermodynamically advantageous sulfion oxidation reaction(SOR)enables the S^(2-)pollutants recovery while reducing the energy input of water electrolysis.Here,a nanoporous NiMo alloy ligament(np-NiMo)with AlNi_(3)/Al_(5)Mo heterostructure was prepared for hydrogen evolution reaction(HER,-0.134V versus reversible hydrogen electrode(vs.RHE)at 50mA/cm^(2)),which needs an Al_(89)Ni_(10)Mo_(1)as a precursor and dealloying operation.Further,the np-NiMo alloy was thermal-treated with S powder to generate Mo-doped NiS_(2)(np-NiMo-S)for OER(1.544V vs.RHE at 50mA/cm^(2))and SOR(0.364 V vs.RHE at 50mA/cm^(2)),while still maintaining the nanostructuring advantages.Moreover,for a two-electrode electrolyzer system with np-NiMo cathode(1M KOH+seawater)coupling np-NiMo-S anode(1mol/L KOH+seawater+1 mol/L Na_(2)S),a remarkably ultra-low cell potential of 0.532 V is acquired at 50mA/cm^(2),which is about 1.015 V below that of normal alkaline seawater splitting.The theory calculations confirmed that the AlNi_(3)/Al_(5)Mo heterostructure within np-NiMo promotes H_(2)O dissociation for excellent HER,while the Mo-dopant of np-NiMo-S lowers energy barriers for the rate-determining step from^(*)S_(4)to^(*)S_(8).This work develops two kinds of NiMo alloy with tremendous prominence for achieving energy-efficient hydrogen production from alkaline seawater and sulfur recycling from sulfion-rich sewage.
基金financially supported by the National Natural Science Foundation of China(Nos.52073214 and 22075211)Guangxi Natural Science Fund for Distinguished Young Scholars(No.2024GXNSFFA010008)+5 种基金Natural Science Foundation of Shandong Province(Nos.ZR2023MB049 and ZR2021QB129)China Postdoctoral Science Foundation(No.2020M670483)Science Foundation of Weifang University(No.2023BS11)supported by the open research fund of the Laboratory of Xinjiang Native Medicinal and Edible Plant Resources Chemistry at Kashi Universitysupported by the Tianhe Qingsuo Open Research Fund of TSYS in 2022 and NSCC-TJNankai University Large-scale Instrument Experimental Technology R&D Project(No.21NKSYJS09)。
文摘Unraveling the essence of electronic structure effected by d-d orbital coupling of transition metal and methanol oxidation reaction(MOR)performance can fundamentally guide high efficient catalyst design.Herein,density functional theory(DFT)calculations were performed at first to study the d–d orbital interaction of metallic Pt Pd Cu,revealing that the incorporation of Pd and Cu atoms into Pt system can enhance d-d electron interaction via capturing antibonding orbital electrons of Pt to fill the surrounding Pd and Cu atoms.Under the theoretical guidance,Pt Pd Cu medium entropy alloy aerogels(Pt Pd Cu MEAAs)catalysts have been designed and systematically screened for MOR under acid,alkaline and neutral electrolyte.Furthermore,DFT calculation and in-situ fourier transform infrared spectroscopy analysis indicate that Pt Pd Cu MEAAs follow the direct pathway via formate as the reactive intermediate to be directly oxidized to CO_(2).For practical direct methanol fuel cells(DMFCs),the Pt Pd Cu MEAAs-integrated ultra-thin catalyst layer(4–5μm thickness)as anode exhibits higher peak power density of 35 m W/cm^(2) than commercial Pt/C of 20 m W/cm^(2)(~40μm thickness)under the similar noble metal loading and an impressive stability retention at a 50-m A/cm^(2) constant current for 10 h.This work clearly proves that optimizing the intermediate adsorption capacity via d-d orbital coupling is an effective strategy to design highly efficient catalysts for DMFCs.
基金financially supported by National Natural Science Foundation of China(22208137 and 22068022)Yunnan Fundamental Research Projects(202101BE070001-033,202401AT070825,202201BE070001007 and 202301AV070005)。
文摘Concurrent activation of lattice oxygen(O_L)and molecular oxygen(O_(2))is crucial for the efficient catalytic oxidation of biomass-derived molecules over metal oxides.Herein,we report that the introduction of ultralow-loading of Ru single atoms(0.42 wt%)into Mn_(2)O_(3)matrix(0.4%Ru-Mn_(2)O_(3))greatly boosts its catalytic activity for the aerobic oxidation of 5-hydroxymethylfurfural(HMF)to 2,5-furandicarboxylic acid(FDCA).The FDCA productivity over the 0.4%Ru-Mn_(2)O_(3)(5.4 mmol_(FDCA)g_(cat)h^(-1))is 4.9 times higher than the Mn_(2)O_(3).Especially,this FDCAproductivity is also significantly higher than that of existing Ru and Mn-based catalysts.Experimental and theoretical investigations discovered that the Ru single atom facilitated the formation of oxygen vacancy(O_(v))in the catalyst,which synergistically weakened the Mn-O bond and promoted the activation of O_L.The co-presence of Ru single atoms and O_(v)also promote the adsorption and activation of both O_(2)and HMF.Consequently,the dehydrogenation reaction energy barrier of the rate-determining step was reduced via both the O_L and chemisorbed O_(2)dehydrogenation pathways,thus boosting the catalytic oxidation reactions.
基金financially supported by the National Natural Science Foundation of China(Nos.22205196 and U1904215)the Natural Science Foundation of Jiangsu Province(No.BK20210790)the start-up fundings from Yangzhou University
文摘Electrochemically induced surface reconstruction offers a novel approach for in situ modulation of the surface structure of nanomaterials.However,comprehensive studies on the surface reconstruction behavior of nanomaterials under diverse electrochemical operations remain limited.Here,exemplified by three electrochemical operations,including cyclic voltammetry(CV),squarewave potential(SWP)and chronoamperometry(CA),we reveal the structural evolution behavior and the corresponding electrocatalytic activity of bimetallic telluride hollow nanorods(Ir_(1-x)Ru_(x)0Te_(2)HNRs).It was found that the surface Te atoms in Ir_(1-x)Ru_(x)0Te_(2)HNRs undergo preferential leaching during the CV and SWP processes,ultimately leading to the formation of a metal alloy shell.In contrast,during the CA process,the surface reconstruction induced by Te leaching was suppressed by the adsorption of anions on the electrode surface.Electrocatalytic tests show that the CV activated Ir_(0.75)Ru_(0.25)Te_(2)HNRs exhibit excellent activity for the hydrogen oxidation reaction in 0.1 M KOH,with a mass activity of 686 Ag^(-1)at an overpotential of50 mV,which is 2.9 times higher than that of commercialPt/C catalyst.Density functional theory(DFT)computation reveals that the incorporation of Ru optimizes the hydroxyl binding energy of IrRu alloy,thus resulting in the reduced reaction energy barrier of hydrogen oxidation reaction.This work provides a new insight into the design of efficient catalysts through electrochemical surface engineering.
基金supported by the National Natural Science Foundation of China(22272103)the China Postdoctoral Science Foundation(2023TQ0204)+3 种基金the Fundamental Research Funds for the Central Universities(GK202304011)the Natural Science Foundation of Shaanxi Province(JC-YBQN-0088)the Science and Technology Innovation Team of Shaanxi Province(2023-CX-TD-27)the Sanqin scholars innovation teams in Shaanxi Province,China。
文摘Highly active and stable electrocatalysts for ethanol oxidation reaction(EOR)are critical for the widespread adoption of direct ethanol fuel cells(DEFCs).However,the low efficiency of C–C bond cleavage of commercial electrocatalysts not only leads to incomplete ethanol oxidation but also results in the accumulation of poisoning CO species.In this work,silver-platinum hollow nanocubes(AgPt hNCs)are designed and synthesized to achieve high selectivity for the complete 12-electron EOR in an alkaline electrolyte.AgPt h NCs demonstrate a Faradaic efficiency of up to 88.2%at the potential of 0.70 V for the C1 pathway and exhibit a 6.3-fold EOR mass activity than commercial Pt black at the potential of 0.81 V.Moreover,the oxyphilic nature of Ag imparts exceptional long-term stability to AgPt h NCs.Theoretical calculations reveal that the electronic interaction between Pt and Ag effectively modifies the d-band properties of surface Pt atoms,thereby optimizing the adsorption behavior of key intermediates,promoting the dehydrogenation of CH_(3)CO^(*)to CH_(2)CO^(*),and facilitating C–C bond cleavage.The present work provides both theoretical and experimental insights into the utilization of Ag-based alloy catalysts for highperformance DEFCs.
基金financially supported by the National Natural Science Foundation of China(Nos.21776115 and 51902140)the project from Key Laboratory of Advanced Technology for Materials Synthesis and Processing(Wuhan University of Technology,No.2024-KF-24)the open project from Key Laboratory of Advanced Electrode Materials for Novel Solar Cells for Petroleum and Chemical Industry of China(School of Chemistry and Life Science,Suzhou University of Science and Technology)
文摘Interface engineering is a prospective method for improving electrochemical performance,while efficient interfacial tuning is still difficult.Here,a series of WO_(3)-Ir catalysts with tuned interfaces were obtained from WO_(3)support with different surface states.The prepared WO_(3)-O-Ir catalyst with higher interfacial oxygen content shows excellent hydrogen oxidation reaction activity with a mass activity of 54.04 A gIr^(-1)for hydrogen oxidation reaction,which is superior to WO_(3)-W-Ir with higher tungsten content and even commercial Pt/C catalysts.Theoretical calculation and X-ray photoelectron spectroscopy valence band spectrum analyses verify that the position of the d-band center is directly proportional to the interfacial oxygen content.This modulates the electronic structure of the active phase,increasing the binding energy for OH species and enhancing their adsorption capacity,which boost the performance for hydrogen oxidation reaction.
基金supported by Jilin Province Science and Technology Development Program(Nos.20200201001JC,20210502002ZP,20230101367JC,20220301011GX)Jilin Province Science and Technology Major Project(No.222648GX0105103875).
文摘The development of efficient and robust non-precious metal electrocatalyst to drive the sluggish hydrogen oxidation reaction(HOR)is the key to the practical application of anion exchange membrane fuel cells(AEMFC),which relies on the rational regulation of intermediates’binding strength.Herein,we reported a simple strategy to manipulate the adsorption energy of OH^(∗)on electrocatalyst surface via engineering Ni/NbO_(x) heterostructures with manageable oxygen vacancy(Ov).Theoretical calculations confirm that the electronic effect between Ni and NbO_(x) could weaken the hydrogen adsorption on Ni,and the interfacial oxygen vacancy tailor hydroxide binding energy(OHBE).The optimized HBE and OHBE contribute to reduce formation energy of water during the alkaline HOR process.Furthermore,in situ Raman spectroscopy monitor the dynamic process that OH^(∗)adsorbed on oxygen vacancy and react with adjacent H^(∗)adsorbed Ni,confirming the vital role of OH^(∗)for alkaline HOR process.As a result,the optimal Ni/NbO_(x) exhibits a remarkable intrinsic activity with a specific activity of 0.036mA/cm^(2),which is 4-fold than that of pristine Ni counterpart and surpasses most non-precious electrocatalysts ever reported.
文摘Active and poisoning-resistant Ru-based electrocatalysts for the hydrogen oxidation reaction(HOR)are designed and fabricated by integrating Cu/Ru dual single atoms and alloy CuRu nanoparticles(N-(CuRu)_(NP+SA)@NC)through a strategy involving weak chemical reduction and ammonia-assisted gas-phase nitridation.The resultant N-(CuRu)_(NP+SA)@NC electrocatalysts feature nitrogen atoms coordinated to both Cu and Ru metal atoms via strong N-metal interactions.Density functional theory calculations revealed that alloyed CuRu nanoparticles and monodispersed Cu atoms are vital for altering the electronic configuration of the host Ru elements.This finely tuned structure enhanced the adsorption of H and OH and promoted CO oxidation over the N-(CuRu)_(NP+SA)@NC electrocatalyst,resulting in high alkaline HOR activity,as evidenced by the higher exchange current density of 3.74 mA cm^(-2)and high mass activity of 3.28 mAμg_(Ru)^(-1),which are far superior to those of most Ru-based catalysts reported to date.Moreover,the N-(CuRu)_(NP+SA)@NC electrocatalysts are resistant to CO poisoning and can be used at a high concentration of 1000 ppm CO with no distinct decay in the activity,in stark contrast to the commercial Pt/C catalyst under the same conditions.
文摘Ethylene glycol(EG)is a biomass derivative of polyethylene terephthalate(PET),and its electrocatalytic conversion into high-value chemicals has sparked widespread interest.This study reviews the most recent research development in electrocatalysis-based EG to glycolic acid(GA)conversion.Firstly,the strategies and research results of modulating the electronic structure of catalysts for efficient selective GA production from EG are reviewed.Second,by reviewing the data of in-situ Fourier transform infrared spectroscopy and in-situ electrochemically attenuated total reflection surface enhanced infrared absorption spectroscopy,the reaction pathway and catalytic mechanism of EG partial oxidation to GA were clarified.Finally,the design and regulation of catalysts for selective oxidation of EG by electrocatalysis in the future are prospected.
基金supported by the National Key Research and Development Program of China,China(2023YFB4006202)the National Natural Science Foundation of China,China(22272206)the Natural Science Foundation of Hunan Province,China(2023JJ10061).
文摘Storing hydrogen in green methanol is a well-known and cost-effective way for long-term energy storage.However,using green methanol in fuel cell technologies requires electrocatalysts with superior resistance to poisoning induced by intermediate species.This study introduces a new class of palladium-based rare earth(RE)alloys with exceptional resistance to methanol for the oxygen reduction reaction(ORR)and outstanding resistance to carbon monoxide poisoning for the hydrogen oxidation reaction(HOR).The PdEr catalyst achieved unparalleled ORR activity amongst the Pd-based rare earth alloys and demonstrated remarkable resistance to methanol poisoning,which is two orders of magnitude higher than commercial Pt/C catalysts.Furthermore,the PdEr catalyst shows high hydrogen oxidation activity under 100 ppm CO.Comprehensive analysis demonstrates that the RE element-enriched sublayer tuning of the Pd-skin's surface strain is responsible for the enhanced ORR and HOR capabilities.This modification allows for precise control over the adsorption strength of critical intermediates while concurrently diminishing the adsorption energy of methanol and CO on the PdEr surface.
