MXene,the two-dimensional transition metal carbide or nitride material,was first discovered in 2011.They possess superior characteristics such as stability,electric conductivity,and electrochemical properties,that mak...MXene,the two-dimensional transition metal carbide or nitride material,was first discovered in 2011.They possess superior characteristics such as stability,electric conductivity,and electrochemical properties,that make them attract the attention of the energy engineering field.Overall water splitting which generates hydrogen and oxygen,not only serves as a clean energy supply technology but also demonstrates the capacity for redistribution and integration of renewable energy.MXene based non-noble metal has demonstrated significant potential in terms of cost-effectiveness.Therefore,the current focus is implementing targeted regulation at the micro level to render it effective comparable to the precious metals.In this context,the mechanisms of the hydrogen evolution reaction(HER) and the oxygen evolution reaction(OER) under the influence of MXene can be elucidated in terms of electron and ion transfer processes,hydrogen coverage,and regulation of terminal groups.Certainly,the composition,structure,synthesis,and stability strategies of MXene are the subjects of comprehensive investigation from both theoretical calculations using density functional theory(DFT) and experimental perspectives.In addition,this review provides a comprehensive summary of MXene based non-noble metal and various modification methods.These methods encompass doping,vacancy engineering,hybrid structures,heterojunction formation,multi-scale engineering,surface engineering,and phase engineering.The review also presents suggestions for designing high-performance MXene based on non-noble metals.It offers guidance on employing construction strategies for electrocatalysts.By leveraging the unique properties and tunability of MXene and implementing these modification methods,researchers can enhance the catalytic activity,stability,selectivity,and efficiency of MXene based non-noble metal catalysts.展开更多
A non-noble metal oxygen reduction reaction (ORR) catalyst labeled as Co-C-N(800) was synthesized by heat-treating a mixture of urea, cobalt chloride and acetylene black for 2 h at 800 ℃ in an inert nitrogen atmo...A non-noble metal oxygen reduction reaction (ORR) catalyst labeled as Co-C-N(800) was synthesized by heat-treating a mixture of urea, cobalt chloride and acetylene black for 2 h at 800 ℃ in an inert nitrogen atmosphere. X-ray diffraction pattern indicates that a metallic β-Co is generated after the heat-treating process. The results from cyclic voltammograms show that the obtained Co-C-N(800) catalyst has good ORR catalytic activity in 0.5 mol/L H2SO4 solution. The catalyst is also good at methanol tolerance and stability in the acidic solution.展开更多
Oxygen electrocatalysts are of great importance for the air electrode in zinc-air batteries(ZABs).Owing to the high specific surface area,controllable pore size and unsaturated metal active sites,metal-organic framewo...Oxygen electrocatalysts are of great importance for the air electrode in zinc-air batteries(ZABs).Owing to the high specific surface area,controllable pore size and unsaturated metal active sites,metal-organic frameworks(MOFs)derivatives have been widely studied as oxygen electrocatalysts in ZABs.To date,many strategies have been developed to generate efficient oxygen electrocatalysts from MOFs for improving the performance of ZABs.In this review,the latest progress of the MOF-derived non-noble metal-oxygen electrocatalysts in ZABs is reviewed.The performance of these MOF-derived catalysts toward oxygen reduction,and oxygen evolution reactions is discussed based on the categories of metal-free carbon materials,single-atom catalysts,metal cluster/carbon composites and metal compound/carbon composites.Moreover,we provide a comprehensive overview on the design strategies of various MOF-derived non-noble metal-oxygen electrocatalysts and their structure-performance relationship.Finally,the challenges and perspectives are provided for further advancing the MOF-derived oxygen electrocatalysts in ZABs.展开更多
Designing low-cost and high-performance photoelectrodes with improved light harvesting and charge separation rates is significant in photoelectrochemical water splitting.Here,a novel TiO2/Cu2O/Al/Al2O3 photoelectrode ...Designing low-cost and high-performance photoelectrodes with improved light harvesting and charge separation rates is significant in photoelectrochemical water splitting.Here,a novel TiO2/Cu2O/Al/Al2O3 photoelectrode is manufactured by depositing plasmonic nanoparticles of the non-noble metal Al on the surface of a TiO2/Cu2O core/shell heterojunction for the first time.The Al nanoparticles,which exhibit a surface plasmon resonance(SPR)effect and are substantially less expensive than noble metals such as Au and Ag,generate hot electron-hole pairs and amplify the electromagnetic field at the interface under illumination.The as-prepared TiO2/Cu2O/Al/Al2O3 photoelectrodes have an extended absorption range and enhanced carrier separation and transfer.Their photocurrent density of 4.52 mA·cm^-2 at 1.23 V vs.RHE represents an 1.84-fold improvement over that of TiO2/Cu2O.Specifically,the ultrathin Al2O3 passivation layer spontaneously generated on the surface of Al in air could act as a protective layer to significantly increase its stability.In this work,the synergistic effect of the heterojunctions and the SPR effect of the non-noble metal Al significantly improve the photoelectrode performance,providing a novel concept for the design of electrodes with good properties and high practicability.展开更多
The non-noble metal modified sulfated zirconia was found easy to deactivate.Herein,highly active and highly stable non-noble core-shell Ni-S_(2)O_(8)^(2−)/Al_(2)O_(3)@ZrO_(2) catalysts(Ni-SA@Z-x,x=Al content in wt%)ha...The non-noble metal modified sulfated zirconia was found easy to deactivate.Herein,highly active and highly stable non-noble core-shell Ni-S_(2)O_(8)^(2−)/Al_(2)O_(3)@ZrO_(2) catalysts(Ni-SA@Z-x,x=Al content in wt%)have been successfully prepared and investigated for n-pentane isomerization.The results showed that the core-shell Ni-SA@Z-30 provided a sustained high isopentane yield(63.1%)with little or no deactivation within 5000 min at a mild reaction pressure of 2.0 MPa,which can be attributed to the following factors:(i)carbon deposition was greatly suppressed by the large pore size and huge pore volume;(ii)the loss of sulfur entities was suppressed because the small and highly dispersed tetragonal ZrO_(2) particles can bond with the S species strongly;(iii)strong Brønsted acidity can be maintained well after the isomerization.The pore structures and acid nature of the core-shell Ni-SA@Z-x are entirely different from those of the normal structure Ni-S_(2)O_(8)^(2−)/ZrO_(2)-Al_(2)O_(3),even though the Al content and the compositions of the individual components are the same.The Al_(2)O_(3)cores endow the catalysts with high internal surface area and high mechanical strength.Meanwhile,the ZrO_(2) shell,which consists of more and smaller tetragonal ZrO_(2) particles because of the large surface area of the Al_(2)O_(3)core,promotes the formation of more stable sulfur species and stronger binding sites.展开更多
The direct electrolytic splitting of abundant seawater instead of scarce freshwater is an ideal strategy for producing clean and renewable hydrogen(H 2)fuels.The oxygen evolution reaction(OER)is a vital half-reaction ...The direct electrolytic splitting of abundant seawater instead of scarce freshwater is an ideal strategy for producing clean and renewable hydrogen(H 2)fuels.The oxygen evolution reaction(OER)is a vital half-reaction that occurs during electrochemical seawater splitting.However,OER suffers from sluggish four-electron transfer kinetics and competitive chlorine evolution reactions in seawater.Noble metal-based catalysts such as IrO_(2) and RuO_(2) are considered to have state-of-the-art OER electrocatalytic activity,but the low reserves and high prices of these noble metals significantly limit their large-scale application.Recently,efforts have been made to explore efficient,robust,and anti-chlorine-corrosion non-noble-metal OER electrocatalysts for seawater splitting such as oxides,hydroxides,phosphides,nitrides,chalcogenides,alloys,and composites.An in-depth understanding of the fundamentals of seawater electrolysis and the design principle of electrode materials is important for promoting seawater-splitting technology.In this review,we first introduce fundamental reactions in seawater electrolytes.Subsequently,construction strategies for OER electrocatalysts for seawater splitting are introduced.Finally,present challenges and perspectives regarding non-noble-metal OER electrocatalysts for commercial H 2 production by seawater splitting are discussed.展开更多
In recent years,many effective photocatalysts have been developed to solve the problem of environmental pollution and clean energy shortage.In this paper,non-noble metal cocatalyst Ni_(3)N nanoparticles supported Zn_(...In recent years,many effective photocatalysts have been developed to solve the problem of environmental pollution and clean energy shortage.In this paper,non-noble metal cocatalyst Ni_(3)N nanoparticles supported Zn_(0.5)Cd_(0.5)S(ZCS)nanorods(Ni_(3)N/ZCS)composites were successfully synthesized by ultrasonic method.The hydrogen production efficiencies of the photocatalysts were tested under visible light,which was found that when the loading of Ni_(3)N was 2%of the mass of ZCS,and the Ni_(3)N/ZCS composite had the best hydrogen evolution performance,which could reach 70.3 mmol·h^(-1)·g^(-1).In addition,the quantum efficiency under 420 nm monochromatic light irradiation was 27.2%.Through different characterization analyses,such as X-ray diffraction(XRD),scanning electron microscopy(SEM),and UV-Vis diffuse reflectance spectra(DRS),a possible photocatalytic mechanism was proposed,providing some reference values for non-precious metals as cocatalysts.展开更多
The realization of efficient oxygen evolution reaction(OER) is critical to the development of multiple sustainable energy conversion and storage technologies, especially hydrogen production via water electrolysis. To ...The realization of efficient oxygen evolution reaction(OER) is critical to the development of multiple sustainable energy conversion and storage technologies, especially hydrogen production via water electrolysis. To achieve the massive application of hydrogen energy and mass-scale hydrogen production from water splitting drives the pursuit of competent precious-metal-free electrocatalysts in acidic media, where the hydrogen evolution reaction(HER) is more facilitated. However, the development of high-efficient and acid-stable OER electrocatalysts, which are robust to function stably at high oxidation potentials in the acidic electrolyte, remains a great challenge. This article contributes a focused, perceptive review of the up-to-date approaches toward this emerging research field. The OER reaction mechanism and fundamental requirements for oxygen evolution electrocatalysts in acid are introduced. Then the progress and new discoveries of precious-metal-free active materials and design concepts with regard to the improvement of the intrinsic OER activity are discussed. Finally, the existing scientific challenges and the outlooks for future research directions to the fabrication of emerging, earth-abundant OER electrocatalysts in acid are pointed out.展开更多
Mixed metal oxides in the nanoscale are of great interest for many aspects of energy related research topics as water splitting, fuel cells and battery technology. The development of scalable, cost-efficient and robus...Mixed metal oxides in the nanoscale are of great interest for many aspects of energy related research topics as water splitting, fuel cells and battery technology. The development of scalable, cost-efficient and robust synthetic routes toward well-defined solid state structures is a major objective in this field.While monometallic oxides have been studied in much detail, reliable synthetic recipes targeting specific crystal structures of mixed metal oxide nanoparticles are largely missing. Yet, in order to meet the requirements for a broad range of technical implementation it is necessary to tailor the properties of mixed metal oxides to the particular purpose. Here, we present a study on the impact of the nature of the gas environment on the resulting crystal structure during a post-synthesis thermal heat treatment of manganese–cobalt oxide nanoparticles. We monitor the evolution of the crystal phase structure as the gas atmosphere is altered from pure nitrogen to synthetic air and pure oxygen. The particle size and homogeneity of the resulting nanoparticles increase with oxygen content, while the crystal structure gradually changes from rocksalt-like to pure spinel. We find the composition of the particles to be independent of the gas atmosphere. The manganese–cobalt oxide nanoparticles exhibited promising electrocatalytic activity regarding oxygen evolution in alkaline electrolyte. These findings offer new synthesis pathways for the direct preparation of versatile utilizable mixed metal oxides.展开更多
Ammonia nitrogen (NH_(4)^(+)-N) is a ubiquitous environmental pollutant,especially in offshore aquaculture systems.Electrochemical oxidation is very promising to remove NH_(4)^(+)-N,but suffers from the use of preciou...Ammonia nitrogen (NH_(4)^(+)-N) is a ubiquitous environmental pollutant,especially in offshore aquaculture systems.Electrochemical oxidation is very promising to remove NH_(4)^(+)-N,but suffers from the use of precious metals anodes.In this work,a robust and cheap electrocatalyst,iron single-atoms distributed in nitrogen-doped carbon (Fe-SAs/N-C),was developed for electrochemical removal of NH_(4)^(+)-N from in wastewater containing chloride.The FeSAs/N-C catalyst exhibited superior activity than that of iron nanoparticles loaded carbon(Fe-NPs/N-C),unmodified carbon and conventional Ti/IrO_(2)-TiO_(2)-RuO_(2)electrodes.And high removal efficiency (>99%) could be achieved as well as high N_(2)selectivity (99.5%) at low current density.Further experiments and density functional theory (DFT) calculations demonstrated the indispensable role of single-atom iron in the promoted generation of chloride derived species for efficient removal of NH_(4)^(+)-N.This study provides promising inexpensive catalysts for NH_(4)^(+)-N removal in aquaculture wastewater.展开更多
The non-noble metal oxygen reduction reaction(ORR) catalysts prepared by carbonization of metal–organic framework(MOF) have attracted more and more attentions in the fields of fuel cells and metal-air batteries due t...The non-noble metal oxygen reduction reaction(ORR) catalysts prepared by carbonization of metal–organic framework(MOF) have attracted more and more attentions in the fields of fuel cells and metal-air batteries due to their unique intrinsic advantages such as high catalytic activity, low price, simple synthesis and good adaptability. Different from the study of traditional high active noble metal catalysts, this review systematically summarizes recent developments on non-noble metal(Fe,Co, Cu, Ni, Mn and Mo) ORR catalysts prepared by various MOFs carbonization in different metal centers. The effects of synthesis strategies and pyrolysis conditions on the catalyst properties are discussed. Meanwhile, the key parameters of catalytic performances(including active sites, dispersed state and specific surface area) are discussed and the prospect is presented. It is expected that this review will provide effective guidance for future studies on carbonized non-noble MOFs for ORR electrochemical catalyst.展开更多
The excessive emission of CO_(2) has caused many environmental issues and is severely threatening the eco-system.CO_(2) electroreduction reaction(CO_(2) RR) that driven by sustainable power is an ideal route for reali...The excessive emission of CO_(2) has caused many environmental issues and is severely threatening the eco-system.CO_(2) electroreduction reaction(CO_(2) RR) that driven by sustainable power is an ideal route for realizing the net reduction of CO_(2) and carbon recycle.Developing efficient electrocatalysts with low cost and high performance is critical for the wide applications of CO_(2) RR electrolysis.Among the various explored CO_(2) RR catalysts,non-noble metal(NNM)-based nanomaterials have drawn increasing attentions due to the remarkable performance and low cost.In this mini-review,the recent advances of NNM-based CO_(2) RR catalysts are summarized,and the catalysts are classified based on their corresponding reduction products.The preparation strategies for engineering the electrocatalysts are introduced,and the relevant CO_(2) RR mechanisms are discussed in detail.Finally,the current challenges in CO_(2) RR research are presented,and some perspectives are proposed for the future development of CO_(2) RR technology.This mini-review introduces the recent advances and frontiers of NNM-based CO_(2) RR catalysts,which should shed light on the further exploration of efficient CO_(2) RR electrocatalysts.展开更多
Hydrogen is a promising candidate for clean and sustainable energy resources to substitute fossil fuels to mitigate global environmental issues.Electrochemical hydrogen production has been regarded as a viable and pro...Hydrogen is a promising candidate for clean and sustainable energy resources to substitute fossil fuels to mitigate global environmental issues.Electrochemical hydrogen production has been regarded as a viable and promising strategy.The overall water splitting is currently the predominant electrochemical hydrogen production method,which could be driven by renewable energy to achieve sustainable production.However,the current challenges are the intrinsically sluggish and energy-intensive oxygen evolution reduction(OER)at the anode and the expensive noble metal-based catalysts for overall water splitting,which limit the practical applications.Extensive efforts have been made to develop bifunctional non-noble metal-based electrocatalysts to boost hydrogen production efficiency and lower the cost.Meanwhile,alternative oxidation reactions with faster kinetics and less energy requirement than OER are being explored as the anodic reaction to couple with the hydrogen evolution reaction for energy-saving hydrogen production.In this review,the non-noble metal-based bifunctional electrocatalysts for overall water splitting,as well as other novel energy-saving hydrogen productions have been introduced and summarized.Current challenges and outlooks are commented on at the end of the article.展开更多
The design and synthesis of highly active non-noble metal oxide catalysts, such as transition- and rare-earth-metal oxides, have attracted significant attention because of their high efficiency and low cost and the re...The design and synthesis of highly active non-noble metal oxide catalysts, such as transition- and rare-earth-metal oxides, have attracted significant attention because of their high efficiency and low cost and the resultant potential applications for the degradation of volatile organic compounds(VOCs). The structure-activity relationships have been well-studied and used to facilitate design of the structure and composition of highly active catalysts. Recently, non-noble metal oxides with porous structures have been used as catalysts for deep oxidation of VOCs, such as aromatic hydrocarbons, aliphatic compounds, aldehydes, and alcohols, with comparable activities to their noble metal counterparts. This review summarizes the growing literature regarding the use of porous metal oxides for the catalytic removal of VOCs, with emphasis on design of the composition and structure and typical synthetic technologies.展开更多
The present work is aimed to improve the performance of Ni-based catalysts for biogas dry reforming by adding a second non-noble metal (Fe, Co, Cu) into a previously studied mesoporous Ni-CaO-ZrO2 nanocomposite. Bio...The present work is aimed to improve the performance of Ni-based catalysts for biogas dry reforming by adding a second non-noble metal (Fe, Co, Cu) into a previously studied mesoporous Ni-CaO-ZrO2 nanocomposite. Biogas was simulated with equivalent methane and carbon dioxide for the dry reforming reaction. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N2 adsorption, temperature-programmed reduction (TPR), thermogravi- metric analysis (TGA), and transmission electron microscopy (TEM) measurements were taken to characterize the structural and textual properties of the bimetallic catalysts as well as the accumulated carbon deposition. The addition of Fe leads to a less ordering growth of mesopores of Fe-Ni-CaO-ZrO2 sample, and the existence of Cu results in a relatively larger portion of free NiO in Cu-Ni-CaO-ZrO2. Compared with Fe and Cu, the presence of Co could efficiently form a beneficial dual metal effect and enhance the strong metal support interaction between Ni and CaO-ZrO2, thus enhancing the activity and stability of the catalyst in biogas dry reforming reaction.展开更多
Geometric and electronic structures of phosphotungstic acid(PTA)supported single transition metal atom(Fe,Co,Ni,Ru,Rh,Pd,Os,Ir and Pt)catalysts have been systematically investigated by using the first-principles theor...Geometric and electronic structures of phosphotungstic acid(PTA)supported single transition metal atom(Fe,Co,Ni,Ru,Rh,Pd,Os,Ir and Pt)catalysts have been systematically investigated by using the first-principles theoretical methods.Possible reaction mechanism for ethylene epoxidation was explored.The most possible anchoring site for the single transition metal atom is the fourfold hollow site on PTA.As the non-noble metal Fe1-PTA system possesses considerable adsorption energies towards both O2 and C2H4,the strong bonding interaction between Fe1 and PTA cluster was analyzed.It is found that the electron transfers from Fe atom to PTA cluster and strong covalent metal-support interactions(CMSI)between the Fe 3 d orbitals and O 2 p orbitals of PTA lay the foundation of high stability.The proposed catalytic reaction mechanism for ethylene epoxidation on Fe1-PTA single-atom catalyst(SAC)includes three steps:the O2 adsorbs on Fe1-PTA via electron transfer;the first ethylene attacks the adsorbed O2 molecule on Fe1-PTA followed by the formation of C2H4O;finally,the O atom remained on Fe1-PTA reacts with a second ethylene to form the product and accomplish the catalytic cycle.The Fe1-PTA has high selectivity and catalytic activity for ethylene epoxidation via an Eley–Rideal mechanism with low energy barriers.A potentially competitive pathway for the formation of acetaldehyde is not kinetically favorable.These results provide insights for the development of highly efficient heterogeneous SACs for ethylene epoxidation with non-noble metals.展开更多
Alkaline water electrolysis is an environmentally friendly and promising approach to produce hydrogen.However,high cost,low efficiency,and poor stability are roadblocks to commercialization of electrocatalysts.This wo...Alkaline water electrolysis is an environmentally friendly and promising approach to produce hydrogen.However,high cost,low efficiency,and poor stability are roadblocks to commercialization of electrocatalysts.This work aims to design and develop a highly efficient,durable,and cost-effective electrocatalyst toward water splitting through modifying metal–organic frameworks.The electrocatalytic performance and stability surpass those of noble metal benchmarks at high current density(1–10 A·cm^(−2)).Theoretical calculations and in situ Raman spectra reveal the electronic structure of the synthesized catalyst and the mechanism of the catalytic reaction process,which rationalizes that the high catalytic activity and stability at high current are attributed to the unique electronic structure of cobalt regulated by copper and the protection provided by carbon nanotubes formed in situ,respectively.In addition,this paper proposes that the desorption ability of the catalyst toward the products(H_(2)and O_(2)),rather than the adsorption ability toward the reactants(H^(+)or OH^(−)),is more important to the sustainable and stable electrochemical water splitting progress at high current density,which is a kinetic rather than thermodynamic dominating process.The findings provide alternative insights to design and employ high performance catalysts to fuel hydrogen production as a clean energy source to tackle the global energy crisis.展开更多
Downsizing noble metal nanoparticles,such as Pt,is an essential goal for many catalytic reactions.A non-noble metal sacrificial approach was used to immobilize monodispersed Pt nanoparticles (NPs) with a mean size o...Downsizing noble metal nanoparticles,such as Pt,is an essential goal for many catalytic reactions.A non-noble metal sacrificial approach was used to immobilize monodispersed Pt nanoparticles (NPs) with a mean size of 1.2 nm on reduced graphene oxide (RGO).ZnO co-precipitated with Pt NPs and subsequently sacrificed by acid etching impedes the diffusion of Pt atoms onto the primary Pt particles and also their aggregation during the reduction of precursors.The resulting ultrafine Pt nanoparticles exhibit high activity (a turnover frequency of 284 min-1 at 298 K) in the hydrolytic dehydrogenation of ammonia borane.The non-noble metal sacrificial approach is demonstrated as a general approach to synthesize well-dispersed noble metal NPs for catalysis.展开更多
Proton exchange membrane fuel cell(PEMFC)has important implications for the success of clean transportation in the future.One of the key factors affecting the cost and performance of PEMFC is the cathode electrocataly...Proton exchange membrane fuel cell(PEMFC)has important implications for the success of clean transportation in the future.One of the key factors affecting the cost and performance of PEMFC is the cathode electrocatalyst for the oxygen reduction reaction(ORR)to overcome sluggish kinetics and instability in an acidic environment.As an essential component of the electrocatalyst,the support material largely determines the activity,mass transfer,charge transfer,and durability of the electrocatalyst.Thereby,the support material plays a critical role in the overall performance of the electrocatalyst.Carbonbased materials are widely used as electrocatalyst supports because of their high porosity,conductivity,chemical stability,and tunable morphology.Recently,some new carbon-based materials with excellent structure have been introduced,such as carbon nanotubes,carbon nanowires,graphene,metal-organic framework(MOF)-derived carbon,and biomass-derived carbon materials.Combined with a variety of strategies,such as controllable construction of porous structures and surface defects,proper doping heteroatoms,the ingenious design of model electrocatalysts,and predictive theoretical calculation,a new reliable path was provided for further improving the performance of electrocatalysts and exploring the catalytic mechanism.Based on the topic of carbon-based materials for ORR in acidic medium,this review summarizes the up-to-date progress and breakthroughs,highlights the factors affecting the catalytic activity and stability of ORR electrocatalysts in acids,and discusses their future application and development.展开更多
Urea oxidation reaction(UOR)is an auxiliary water electrolysis hydrogen production technology developed in recent years to replace oxygen evolution reaction and reduce energy consumption,which can produce hydrogen mor...Urea oxidation reaction(UOR)is an auxiliary water electrolysis hydrogen production technology developed in recent years to replace oxygen evolution reaction and reduce energy consumption,which can produce hydrogen more efficiently by low theoretical potential,reduce the average cost of electrochemical hydrogen production,and is a frontier research hotspot for renewable hydrogen energy.Two-dimensional(2D)nanomaterials as electrocatalysts have many favorable potential,such as it can effectively reduce the resistivity of materials and increase the specific surface area with certainty.This paper reviews the application of 2D materials in UOR in alkaline electrolytes.And a cross-sectional comparison of various material performance data including overpotential,Tafel slope,electrochemical active surface area(ECSA)and it stability test was conducted,which could illustrate the differences between materials composed of different elements.In addition,the main challenges hindering the progress of research on 2D materials in urea electrocatalysis processes and promising materials in this field in future are summarized and prospected.It is believed that this review will contribute to designing and analyzing highperformance 2D urea electrocatalysts for water splitting.展开更多
基金supported by National Natural Science Foundation of China (Grant No. 22279091)。
文摘MXene,the two-dimensional transition metal carbide or nitride material,was first discovered in 2011.They possess superior characteristics such as stability,electric conductivity,and electrochemical properties,that make them attract the attention of the energy engineering field.Overall water splitting which generates hydrogen and oxygen,not only serves as a clean energy supply technology but also demonstrates the capacity for redistribution and integration of renewable energy.MXene based non-noble metal has demonstrated significant potential in terms of cost-effectiveness.Therefore,the current focus is implementing targeted regulation at the micro level to render it effective comparable to the precious metals.In this context,the mechanisms of the hydrogen evolution reaction(HER) and the oxygen evolution reaction(OER) under the influence of MXene can be elucidated in terms of electron and ion transfer processes,hydrogen coverage,and regulation of terminal groups.Certainly,the composition,structure,synthesis,and stability strategies of MXene are the subjects of comprehensive investigation from both theoretical calculations using density functional theory(DFT) and experimental perspectives.In addition,this review provides a comprehensive summary of MXene based non-noble metal and various modification methods.These methods encompass doping,vacancy engineering,hybrid structures,heterojunction formation,multi-scale engineering,surface engineering,and phase engineering.The review also presents suggestions for designing high-performance MXene based on non-noble metals.It offers guidance on employing construction strategies for electrocatalysts.By leveraging the unique properties and tunability of MXene and implementing these modification methods,researchers can enhance the catalytic activity,stability,selectivity,and efficiency of MXene based non-noble metal catalysts.
文摘A non-noble metal oxygen reduction reaction (ORR) catalyst labeled as Co-C-N(800) was synthesized by heat-treating a mixture of urea, cobalt chloride and acetylene black for 2 h at 800 ℃ in an inert nitrogen atmosphere. X-ray diffraction pattern indicates that a metallic β-Co is generated after the heat-treating process. The results from cyclic voltammograms show that the obtained Co-C-N(800) catalyst has good ORR catalytic activity in 0.5 mol/L H2SO4 solution. The catalyst is also good at methanol tolerance and stability in the acidic solution.
基金This work is supported by the National Natural Science Foundation of China(22075092)the Program for HUST Academic Frontier Youth Team(2018QYTD15).
文摘Oxygen electrocatalysts are of great importance for the air electrode in zinc-air batteries(ZABs).Owing to the high specific surface area,controllable pore size and unsaturated metal active sites,metal-organic frameworks(MOFs)derivatives have been widely studied as oxygen electrocatalysts in ZABs.To date,many strategies have been developed to generate efficient oxygen electrocatalysts from MOFs for improving the performance of ZABs.In this review,the latest progress of the MOF-derived non-noble metal-oxygen electrocatalysts in ZABs is reviewed.The performance of these MOF-derived catalysts toward oxygen reduction,and oxygen evolution reactions is discussed based on the categories of metal-free carbon materials,single-atom catalysts,metal cluster/carbon composites and metal compound/carbon composites.Moreover,we provide a comprehensive overview on the design strategies of various MOF-derived non-noble metal-oxygen electrocatalysts and their structure-performance relationship.Finally,the challenges and perspectives are provided for further advancing the MOF-derived oxygen electrocatalysts in ZABs.
文摘Designing low-cost and high-performance photoelectrodes with improved light harvesting and charge separation rates is significant in photoelectrochemical water splitting.Here,a novel TiO2/Cu2O/Al/Al2O3 photoelectrode is manufactured by depositing plasmonic nanoparticles of the non-noble metal Al on the surface of a TiO2/Cu2O core/shell heterojunction for the first time.The Al nanoparticles,which exhibit a surface plasmon resonance(SPR)effect and are substantially less expensive than noble metals such as Au and Ag,generate hot electron-hole pairs and amplify the electromagnetic field at the interface under illumination.The as-prepared TiO2/Cu2O/Al/Al2O3 photoelectrodes have an extended absorption range and enhanced carrier separation and transfer.Their photocurrent density of 4.52 mA·cm^-2 at 1.23 V vs.RHE represents an 1.84-fold improvement over that of TiO2/Cu2O.Specifically,the ultrathin Al2O3 passivation layer spontaneously generated on the surface of Al in air could act as a protective layer to significantly increase its stability.In this work,the synergistic effect of the heterojunctions and the SPR effect of the non-noble metal Al significantly improve the photoelectrode performance,providing a novel concept for the design of electrodes with good properties and high practicability.
文摘The non-noble metal modified sulfated zirconia was found easy to deactivate.Herein,highly active and highly stable non-noble core-shell Ni-S_(2)O_(8)^(2−)/Al_(2)O_(3)@ZrO_(2) catalysts(Ni-SA@Z-x,x=Al content in wt%)have been successfully prepared and investigated for n-pentane isomerization.The results showed that the core-shell Ni-SA@Z-30 provided a sustained high isopentane yield(63.1%)with little or no deactivation within 5000 min at a mild reaction pressure of 2.0 MPa,which can be attributed to the following factors:(i)carbon deposition was greatly suppressed by the large pore size and huge pore volume;(ii)the loss of sulfur entities was suppressed because the small and highly dispersed tetragonal ZrO_(2) particles can bond with the S species strongly;(iii)strong Brønsted acidity can be maintained well after the isomerization.The pore structures and acid nature of the core-shell Ni-SA@Z-x are entirely different from those of the normal structure Ni-S_(2)O_(8)^(2−)/ZrO_(2)-Al_(2)O_(3),even though the Al content and the compositions of the individual components are the same.The Al_(2)O_(3)cores endow the catalysts with high internal surface area and high mechanical strength.Meanwhile,the ZrO_(2) shell,which consists of more and smaller tetragonal ZrO_(2) particles because of the large surface area of the Al_(2)O_(3)core,promotes the formation of more stable sulfur species and stronger binding sites.
基金supported by the National Key Research and De-velopment Project of China(2022YFE0113800)National Natural Sci-ence Foundation of China(21905246,51972286,and 22005268)+2 种基金Zhe-jiang Provincial Natural Science Foundation of China(LZ21E020003,LR19E020003,LQ21E020004,and LQ20B010011)Fundamental Re-search Funds for the Provincial Universities of Zhejiang(RF-B-2020004)Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(2020R01002).
文摘The direct electrolytic splitting of abundant seawater instead of scarce freshwater is an ideal strategy for producing clean and renewable hydrogen(H 2)fuels.The oxygen evolution reaction(OER)is a vital half-reaction that occurs during electrochemical seawater splitting.However,OER suffers from sluggish four-electron transfer kinetics and competitive chlorine evolution reactions in seawater.Noble metal-based catalysts such as IrO_(2) and RuO_(2) are considered to have state-of-the-art OER electrocatalytic activity,but the low reserves and high prices of these noble metals significantly limit their large-scale application.Recently,efforts have been made to explore efficient,robust,and anti-chlorine-corrosion non-noble-metal OER electrocatalysts for seawater splitting such as oxides,hydroxides,phosphides,nitrides,chalcogenides,alloys,and composites.An in-depth understanding of the fundamentals of seawater electrolysis and the design principle of electrode materials is important for promoting seawater-splitting technology.In this review,we first introduce fundamental reactions in seawater electrolytes.Subsequently,construction strategies for OER electrocatalysts for seawater splitting are introduced.Finally,present challenges and perspectives regarding non-noble-metal OER electrocatalysts for commercial H 2 production by seawater splitting are discussed.
基金supported by the Natural Science Foundation of Jilin Province,China(No.YDZJ202101ZYTS067)the Foundation of Xinzhou Normal University,China(No.2021KY01).
文摘In recent years,many effective photocatalysts have been developed to solve the problem of environmental pollution and clean energy shortage.In this paper,non-noble metal cocatalyst Ni_(3)N nanoparticles supported Zn_(0.5)Cd_(0.5)S(ZCS)nanorods(Ni_(3)N/ZCS)composites were successfully synthesized by ultrasonic method.The hydrogen production efficiencies of the photocatalysts were tested under visible light,which was found that when the loading of Ni_(3)N was 2%of the mass of ZCS,and the Ni_(3)N/ZCS composite had the best hydrogen evolution performance,which could reach 70.3 mmol·h^(-1)·g^(-1).In addition,the quantum efficiency under 420 nm monochromatic light irradiation was 27.2%.Through different characterization analyses,such as X-ray diffraction(XRD),scanning electron microscopy(SEM),and UV-Vis diffuse reflectance spectra(DRS),a possible photocatalytic mechanism was proposed,providing some reference values for non-precious metals as cocatalysts.
基金financial support of the National Natural Science Foundation of China (21962008, 51464028)Candidate Talents Training Fund of Yunnan Province (2017PY269SQ, 2018HB007)Yunnan Ten Thousand Talents Plan Young & Elite Talents Project (YNWR-QNBJ-2018-346)。
文摘The realization of efficient oxygen evolution reaction(OER) is critical to the development of multiple sustainable energy conversion and storage technologies, especially hydrogen production via water electrolysis. To achieve the massive application of hydrogen energy and mass-scale hydrogen production from water splitting drives the pursuit of competent precious-metal-free electrocatalysts in acidic media, where the hydrogen evolution reaction(HER) is more facilitated. However, the development of high-efficient and acid-stable OER electrocatalysts, which are robust to function stably at high oxidation potentials in the acidic electrolyte, remains a great challenge. This article contributes a focused, perceptive review of the up-to-date approaches toward this emerging research field. The OER reaction mechanism and fundamental requirements for oxygen evolution electrocatalysts in acid are introduced. Then the progress and new discoveries of precious-metal-free active materials and design concepts with regard to the improvement of the intrinsic OER activity are discussed. Finally, the existing scientific challenges and the outlooks for future research directions to the fabrication of emerging, earth-abundant OER electrocatalysts in acid are pointed out.
基金supported by the Federal Ministry of Education and Research under the grant reference number 03SF0433A "MEOKATS"
文摘Mixed metal oxides in the nanoscale are of great interest for many aspects of energy related research topics as water splitting, fuel cells and battery technology. The development of scalable, cost-efficient and robust synthetic routes toward well-defined solid state structures is a major objective in this field.While monometallic oxides have been studied in much detail, reliable synthetic recipes targeting specific crystal structures of mixed metal oxide nanoparticles are largely missing. Yet, in order to meet the requirements for a broad range of technical implementation it is necessary to tailor the properties of mixed metal oxides to the particular purpose. Here, we present a study on the impact of the nature of the gas environment on the resulting crystal structure during a post-synthesis thermal heat treatment of manganese–cobalt oxide nanoparticles. We monitor the evolution of the crystal phase structure as the gas atmosphere is altered from pure nitrogen to synthetic air and pure oxygen. The particle size and homogeneity of the resulting nanoparticles increase with oxygen content, while the crystal structure gradually changes from rocksalt-like to pure spinel. We find the composition of the particles to be independent of the gas atmosphere. The manganese–cobalt oxide nanoparticles exhibited promising electrocatalytic activity regarding oxygen evolution in alkaline electrolyte. These findings offer new synthesis pathways for the direct preparation of versatile utilizable mixed metal oxides.
基金supported by the Natural Science Foundation of Hubei Province of China(No. 2020CFB382)the National Natural Science Foundation of China(No. 22176068)the Research and Innovation Initiatives of WHPU(No. 2022J03)。
文摘Ammonia nitrogen (NH_(4)^(+)-N) is a ubiquitous environmental pollutant,especially in offshore aquaculture systems.Electrochemical oxidation is very promising to remove NH_(4)^(+)-N,but suffers from the use of precious metals anodes.In this work,a robust and cheap electrocatalyst,iron single-atoms distributed in nitrogen-doped carbon (Fe-SAs/N-C),was developed for electrochemical removal of NH_(4)^(+)-N from in wastewater containing chloride.The FeSAs/N-C catalyst exhibited superior activity than that of iron nanoparticles loaded carbon(Fe-NPs/N-C),unmodified carbon and conventional Ti/IrO_(2)-TiO_(2)-RuO_(2)electrodes.And high removal efficiency (>99%) could be achieved as well as high N_(2)selectivity (99.5%) at low current density.Further experiments and density functional theory (DFT) calculations demonstrated the indispensable role of single-atom iron in the promoted generation of chloride derived species for efficient removal of NH_(4)^(+)-N.This study provides promising inexpensive catalysts for NH_(4)^(+)-N removal in aquaculture wastewater.
基金financially supported by the National Natural Science Foundation of China (Nos.21873027 and 21908046)Hubei Natural Science Foundation (No.2019CFB293)Ministry-of-Education Key Laboratory for the Synthesis and Application of Organic Functional Molecules (No.KLSAOFM1802)。
文摘The non-noble metal oxygen reduction reaction(ORR) catalysts prepared by carbonization of metal–organic framework(MOF) have attracted more and more attentions in the fields of fuel cells and metal-air batteries due to their unique intrinsic advantages such as high catalytic activity, low price, simple synthesis and good adaptability. Different from the study of traditional high active noble metal catalysts, this review systematically summarizes recent developments on non-noble metal(Fe,Co, Cu, Ni, Mn and Mo) ORR catalysts prepared by various MOFs carbonization in different metal centers. The effects of synthesis strategies and pyrolysis conditions on the catalyst properties are discussed. Meanwhile, the key parameters of catalytic performances(including active sites, dispersed state and specific surface area) are discussed and the prospect is presented. It is expected that this review will provide effective guidance for future studies on carbonized non-noble MOFs for ORR electrochemical catalyst.
基金financially supported by the National Natural Science Foundation of China(Nos.52001227 and 51972224)the China Postdoctoral Science Foundation(No.2019M661014)。
文摘The excessive emission of CO_(2) has caused many environmental issues and is severely threatening the eco-system.CO_(2) electroreduction reaction(CO_(2) RR) that driven by sustainable power is an ideal route for realizing the net reduction of CO_(2) and carbon recycle.Developing efficient electrocatalysts with low cost and high performance is critical for the wide applications of CO_(2) RR electrolysis.Among the various explored CO_(2) RR catalysts,non-noble metal(NNM)-based nanomaterials have drawn increasing attentions due to the remarkable performance and low cost.In this mini-review,the recent advances of NNM-based CO_(2) RR catalysts are summarized,and the catalysts are classified based on their corresponding reduction products.The preparation strategies for engineering the electrocatalysts are introduced,and the relevant CO_(2) RR mechanisms are discussed in detail.Finally,the current challenges in CO_(2) RR research are presented,and some perspectives are proposed for the future development of CO_(2) RR technology.This mini-review introduces the recent advances and frontiers of NNM-based CO_(2) RR catalysts,which should shed light on the further exploration of efficient CO_(2) RR electrocatalysts.
基金financially supported by the National Key R&D Program of China (No. 2021YFA1501101)the National Natural Science Foundation of China (No. NSFC 21771156)the NSFC/RGC Joint Research Scheme Project (N_Poly U502/ 21)
文摘Hydrogen is a promising candidate for clean and sustainable energy resources to substitute fossil fuels to mitigate global environmental issues.Electrochemical hydrogen production has been regarded as a viable and promising strategy.The overall water splitting is currently the predominant electrochemical hydrogen production method,which could be driven by renewable energy to achieve sustainable production.However,the current challenges are the intrinsically sluggish and energy-intensive oxygen evolution reduction(OER)at the anode and the expensive noble metal-based catalysts for overall water splitting,which limit the practical applications.Extensive efforts have been made to develop bifunctional non-noble metal-based electrocatalysts to boost hydrogen production efficiency and lower the cost.Meanwhile,alternative oxidation reactions with faster kinetics and less energy requirement than OER are being explored as the anodic reaction to couple with the hydrogen evolution reaction for energy-saving hydrogen production.In this review,the non-noble metal-based bifunctional electrocatalysts for overall water splitting,as well as other novel energy-saving hydrogen productions have been introduced and summarized.Current challenges and outlooks are commented on at the end of the article.
基金supported by the National High Technology Research and Development Program of China(2012AA062702)the strategic project of the Chinese Academy of Sciences(XDB05050000)
文摘The design and synthesis of highly active non-noble metal oxide catalysts, such as transition- and rare-earth-metal oxides, have attracted significant attention because of their high efficiency and low cost and the resultant potential applications for the degradation of volatile organic compounds(VOCs). The structure-activity relationships have been well-studied and used to facilitate design of the structure and composition of highly active catalysts. Recently, non-noble metal oxides with porous structures have been used as catalysts for deep oxidation of VOCs, such as aromatic hydrocarbons, aliphatic compounds, aldehydes, and alcohols, with comparable activities to their noble metal counterparts. This review summarizes the growing literature regarding the use of porous metal oxides for the catalytic removal of VOCs, with emphasis on design of the composition and structure and typical synthetic technologies.
基金This work has been supported by the grant fiom the National Natural Science Foundation of China (No. 21603127), the Natural Science Foundation of Shanxi Province (No. 201601 D202020), the International S a T Cooperation Program of China (No. 2013DFA40460), and the Talent Development Funds of Shanxi University.
文摘The present work is aimed to improve the performance of Ni-based catalysts for biogas dry reforming by adding a second non-noble metal (Fe, Co, Cu) into a previously studied mesoporous Ni-CaO-ZrO2 nanocomposite. Biogas was simulated with equivalent methane and carbon dioxide for the dry reforming reaction. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N2 adsorption, temperature-programmed reduction (TPR), thermogravi- metric analysis (TGA), and transmission electron microscopy (TEM) measurements were taken to characterize the structural and textual properties of the bimetallic catalysts as well as the accumulated carbon deposition. The addition of Fe leads to a less ordering growth of mesopores of Fe-Ni-CaO-ZrO2 sample, and the existence of Cu results in a relatively larger portion of free NiO in Cu-Ni-CaO-ZrO2. Compared with Fe and Cu, the presence of Co could efficiently form a beneficial dual metal effect and enhance the strong metal support interaction between Ni and CaO-ZrO2, thus enhancing the activity and stability of the catalyst in biogas dry reforming reaction.
基金financially supported by the National Natural Science Foundation of China (21590792, 91426302 and 21433005)Guangdong Provincial Key Laboratory of Catalysis (2020B121201002)+1 种基金the Special Funding for Transformation of Scientific and Technological Achievements in Qinghai Province (2018-GX-101)the Natural Science Basic Research Program of Shaanxi Province (2019JM-226)
文摘Geometric and electronic structures of phosphotungstic acid(PTA)supported single transition metal atom(Fe,Co,Ni,Ru,Rh,Pd,Os,Ir and Pt)catalysts have been systematically investigated by using the first-principles theoretical methods.Possible reaction mechanism for ethylene epoxidation was explored.The most possible anchoring site for the single transition metal atom is the fourfold hollow site on PTA.As the non-noble metal Fe1-PTA system possesses considerable adsorption energies towards both O2 and C2H4,the strong bonding interaction between Fe1 and PTA cluster was analyzed.It is found that the electron transfers from Fe atom to PTA cluster and strong covalent metal-support interactions(CMSI)between the Fe 3 d orbitals and O 2 p orbitals of PTA lay the foundation of high stability.The proposed catalytic reaction mechanism for ethylene epoxidation on Fe1-PTA single-atom catalyst(SAC)includes three steps:the O2 adsorbs on Fe1-PTA via electron transfer;the first ethylene attacks the adsorbed O2 molecule on Fe1-PTA followed by the formation of C2H4O;finally,the O atom remained on Fe1-PTA reacts with a second ethylene to form the product and accomplish the catalytic cycle.The Fe1-PTA has high selectivity and catalytic activity for ethylene epoxidation via an Eley–Rideal mechanism with low energy barriers.A potentially competitive pathway for the formation of acetaldehyde is not kinetically favorable.These results provide insights for the development of highly efficient heterogeneous SACs for ethylene epoxidation with non-noble metals.
基金support by the program for JLU Science and Technology Innovative Research Team(JLUSTIRT).
文摘Alkaline water electrolysis is an environmentally friendly and promising approach to produce hydrogen.However,high cost,low efficiency,and poor stability are roadblocks to commercialization of electrocatalysts.This work aims to design and develop a highly efficient,durable,and cost-effective electrocatalyst toward water splitting through modifying metal–organic frameworks.The electrocatalytic performance and stability surpass those of noble metal benchmarks at high current density(1–10 A·cm^(−2)).Theoretical calculations and in situ Raman spectra reveal the electronic structure of the synthesized catalyst and the mechanism of the catalytic reaction process,which rationalizes that the high catalytic activity and stability at high current are attributed to the unique electronic structure of cobalt regulated by copper and the protection provided by carbon nanotubes formed in situ,respectively.In addition,this paper proposes that the desorption ability of the catalyst toward the products(H_(2)and O_(2)),rather than the adsorption ability toward the reactants(H^(+)or OH^(−)),is more important to the sustainable and stable electrochemical water splitting progress at high current density,which is a kinetic rather than thermodynamic dominating process.The findings provide alternative insights to design and employ high performance catalysts to fuel hydrogen production as a clean energy source to tackle the global energy crisis.
文摘Downsizing noble metal nanoparticles,such as Pt,is an essential goal for many catalytic reactions.A non-noble metal sacrificial approach was used to immobilize monodispersed Pt nanoparticles (NPs) with a mean size of 1.2 nm on reduced graphene oxide (RGO).ZnO co-precipitated with Pt NPs and subsequently sacrificed by acid etching impedes the diffusion of Pt atoms onto the primary Pt particles and also their aggregation during the reduction of precursors.The resulting ultrafine Pt nanoparticles exhibit high activity (a turnover frequency of 284 min-1 at 298 K) in the hydrolytic dehydrogenation of ammonia borane.The non-noble metal sacrificial approach is demonstrated as a general approach to synthesize well-dispersed noble metal NPs for catalysis.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.U1710256 and U1810115)the Shanxi Science and Technology Major Project(Grant Nos.20181102019 and 20201101016)。
文摘Proton exchange membrane fuel cell(PEMFC)has important implications for the success of clean transportation in the future.One of the key factors affecting the cost and performance of PEMFC is the cathode electrocatalyst for the oxygen reduction reaction(ORR)to overcome sluggish kinetics and instability in an acidic environment.As an essential component of the electrocatalyst,the support material largely determines the activity,mass transfer,charge transfer,and durability of the electrocatalyst.Thereby,the support material plays a critical role in the overall performance of the electrocatalyst.Carbonbased materials are widely used as electrocatalyst supports because of their high porosity,conductivity,chemical stability,and tunable morphology.Recently,some new carbon-based materials with excellent structure have been introduced,such as carbon nanotubes,carbon nanowires,graphene,metal-organic framework(MOF)-derived carbon,and biomass-derived carbon materials.Combined with a variety of strategies,such as controllable construction of porous structures and surface defects,proper doping heteroatoms,the ingenious design of model electrocatalysts,and predictive theoretical calculation,a new reliable path was provided for further improving the performance of electrocatalysts and exploring the catalytic mechanism.Based on the topic of carbon-based materials for ORR in acidic medium,this review summarizes the up-to-date progress and breakthroughs,highlights the factors affecting the catalytic activity and stability of ORR electrocatalysts in acids,and discusses their future application and development.
基金financially supported by the National Key Research and Development Program of China(No.2020YFB1713500)the Major Science and Technology Projects of Henan Province(No.221100230200)+3 种基金Program for Innovative Research Team(in Science and Technology)in University of Henan Province(No.23IRTSTHN009)the Project of Science and Technology Department of Henan Province(Nos.232102241034 and 222102240074)the Natural Science Foundation of Suzhou University of Science and Technology(No.XKQ2020002)the Natural Science Foundation of Jiangsu Higher Education Institutions of China(No.22KJB530009)。
文摘Urea oxidation reaction(UOR)is an auxiliary water electrolysis hydrogen production technology developed in recent years to replace oxygen evolution reaction and reduce energy consumption,which can produce hydrogen more efficiently by low theoretical potential,reduce the average cost of electrochemical hydrogen production,and is a frontier research hotspot for renewable hydrogen energy.Two-dimensional(2D)nanomaterials as electrocatalysts have many favorable potential,such as it can effectively reduce the resistivity of materials and increase the specific surface area with certainty.This paper reviews the application of 2D materials in UOR in alkaline electrolytes.And a cross-sectional comparison of various material performance data including overpotential,Tafel slope,electrochemical active surface area(ECSA)and it stability test was conducted,which could illustrate the differences between materials composed of different elements.In addition,the main challenges hindering the progress of research on 2D materials in urea electrocatalysis processes and promising materials in this field in future are summarized and prospected.It is believed that this review will contribute to designing and analyzing highperformance 2D urea electrocatalysts for water splitting.