The incorporation of partial A-site substitution in perovskite oxides represents a promising strategy for precisely controlling the electronic configuration and enhancing its intrinsic catalytic activity.Conventional ...The incorporation of partial A-site substitution in perovskite oxides represents a promising strategy for precisely controlling the electronic configuration and enhancing its intrinsic catalytic activity.Conventional methods for A-site substitution typically involve prolonged high-temperature processes.While these processes promote the development of unique nanostructures with highly exposed active sites,they often result in the uncontrolled configuration of introduced elements.Herein,we present a novel approach for synthesizing two-dimensional(2D)porous GdFeO_(3) perovskite with A-site strontium(Sr)substitution utilizing microwave shock method.This technique enables precise control of the Sr content and simultaneous construction of 2D porous structures in one step,capitalizing on the advantages of rapid heating and cooling(temperature~1100 K,rate~70 K s^(-1)).The active sites of this oxygen-rich defect structure can be clearly revealed through the simulation of the electronic configuration and the comprehensive analysis of the crystal structure.For electrocatalytic oxygen evolution reaction application,the synthesized 2D porous Gd_(0.8)Sr_(0.2)FeO_(3) electrocatalyst exhibits an exceptional overpotential of 294 mV at a current density of 10 mA cm^(-2)and a small Tafel slope of 55.85 mV dec^(-1)in alkaline electrolytes.This study offers a fresh perspective on designing crystal configurations and the construction of nanostructures in perovskite.展开更多
Ni^(2+)/Cu^(2+)/SO_(4)^(2-)/polyvinyl alcohol precursor fibers with uniform diameters were prepared through electrospinning.Nickel-based composite nanoalloys containing Ni,Cu,and S were prepared through heat treatment...Ni^(2+)/Cu^(2+)/SO_(4)^(2-)/polyvinyl alcohol precursor fibers with uniform diameters were prepared through electrospinning.Nickel-based composite nanoalloys containing Ni,Cu,and S were prepared through heat treatment in an Ar atmosphere.The experimental results show that the main components of the prepared nanoalloys are NiCu,Ni_(3)S_(2),Ni,and C.The nanoalloys exhibit fine grain sizes about 200-500 nm,which can increase with increasing heat treatment temperature.Electrochemical test results show that the nickel sulfidemodified NiCu nanoalloy composites exhibit excellent oxygen evolution reaction properties,and the oxygen evolution reaction properties gradually improve with the increasing heat treatment temperature.The sample prepared at 1 000℃ for 40 min show a low overpotential of 423 mV and a small Tafel slope of 134 mV·dec^(-1) at a current density of 10 mA·cm^(-2).展开更多
Constructing highly-efficient electrocatalysts toward hydrogen evolution reaction(HER)/oxygen evolution reaction(OER)/oxygen reduction reaction(ORR)with excellent stability is quite important for the development of re...Constructing highly-efficient electrocatalysts toward hydrogen evolution reaction(HER)/oxygen evolution reaction(OER)/oxygen reduction reaction(ORR)with excellent stability is quite important for the development of renewable energy-related applications.Herein,Co-Ru based compounds supported on nitrogen doped two-dimensional(2D)carbon nanosheets(NCN)are developed via one step pyrolysis procedure(Co-Ru/NCN)for HER/ORR and following low-temperature oxidation process(Co-Ru@RuO_(x)/NCN)for OER.The specific 2D morphology guarantees abundant active sites exposure.Furthermore,the synergistic effects arising from the interaction between Co and Ru are crucial in enhancing the catalytic performance.Thus,the resulting Co-Ru/NCN shows remarkable electrocatalytic performance for HER(70 mV at 10 mA cm^(-2))in 1 M KOH and ORR(half-wave potential E_(1/2)=0.81 V)in 0.1 M KOH.Especially,the Co-Ru@RuO_(x)/NCN obtained by oxidation exhibits splendid OER performance in both acid(230 mV at 10 mA cm^(-2))and alkaline media(270 mV at 10 mA cm^(-2))coupled with excellent stability.Consequently,the fabricated two-electrode water-splitting device exhibits excellent performance in both acidic and alkaline environments.This research provides a promising avenue for the advancement of multifunctional nanomaterials.展开更多
Rational design of oxygen evolution reaction(OER)catalysts at low cost would greatly benefit the economy.Taking advantage of earth-abundant elements Si,Co and Ni,we produce a unique-structure where cobalt-nickel silic...Rational design of oxygen evolution reaction(OER)catalysts at low cost would greatly benefit the economy.Taking advantage of earth-abundant elements Si,Co and Ni,we produce a unique-structure where cobalt-nickel silicate hydroxide[Co_(2.5)Ni_(0.5)Si_(2)O_(5)(OH)_(4)]is vertically grown on a reduced graphene oxide(rGO)support(CNS@rGO).This is developed as a low-cost and prospective OER catalyst.Compared to cobalt or nickel silicate hydroxide@rGO(CS@rGO and NS@rGO,respectively)nanoarrays,the bimetal CNS@rGO nanoarray exhibits impressive OER performance with an overpotential of 307 mV@10 mA cm^(-2).This value is higher than that of CS@rGO and NS@rGO.The CNS@rGO nanoarray has an overpotential of 446 mV@100 mA cm^(-2),about 1.4 times that of the commercial RuO_(2)electrocatalyst.The achieved OER activity is superior to the state-of-the-art metal oxides/hydroxides and their derivatives.The vertically grown nanostructure and optimized metal-support electronic interactions play an indispensable role for OER performance improvement,including a fast electron transfer pathway,short proton/electron diffusion distance,more active metal centers,as well as optimized dualatomic electron density.Taking advantage of interlay chemical regulation and the in-situ growth method,the advanced-structural CNS@rGO nanoarrays provide a new horizon to the rational and flexible design of efficient and promising OER electrocatalysts.展开更多
F-PbO2 electrode and polytetrafluoroethylene (PTFE) doped F-PbO2 electrode (PTFE-F-PbO2) were prepared on a plexiglas sheet substrate by a series of procedure including chemical and electrochemical depositions. Th...F-PbO2 electrode and polytetrafluoroethylene (PTFE) doped F-PbO2 electrode (PTFE-F-PbO2) were prepared on a plexiglas sheet substrate by a series of procedure including chemical and electrochemical depositions. The electrochemical activities of these two electrodes for oxygen evolution (OE) reaction were examined by electrochemical tests. In comparison with F-PbO2, PTFE-F-PbO2 electrode exhibited larger active surface area and higher oxygen vacancy deficiency, which resulted in its higher electrocatalytic activity for OE. In addition, both exchange current density and activation energy of the electrodes for OE were calculated in terms of active surface area. The values of exchange current density and activation energy in 0.5 mol·L^-1 H2SO4 aqueous solution were 1.125×10^ -3 mA·cm^-2 and 18.62 kJ·mol^-1 for PTFE-F-PbO2, and 8.384×10^-4 mA·cm^- 2 and 28.98 kJ·mol^-1 for F-PbO2, respectively. Because these values are calculated on the basis of the active surface areas of the electrodes, the enhanced activity of PTFE-F-PbO2 can be attributed to an increase in oxygen vacancy deficiency of PbO2 due to doping by PTFE. The influence of PTFE adulteration on the activity of PbO2 film electrode for OE was investigated in detail in this study.展开更多
In this study,we prepared Ti/IrO2–ZrO2 electrodes with different ZrO2 contents using zirconium-n-butoxide(C16H36O4Zr)and chloroiridic acid(H2IrCl6)via a sol–gel route.To explore the effect of ZrO2 content on the sur...In this study,we prepared Ti/IrO2–ZrO2 electrodes with different ZrO2 contents using zirconium-n-butoxide(C16H36O4Zr)and chloroiridic acid(H2IrCl6)via a sol–gel route.To explore the effect of ZrO2 content on the surface properties and electrochemical behavior of electrodes,we performed physical characterizations and electrochemical measurements.The obtained results revealed that the binary oxide coating was composed of rutile IrO2,amorphous ZrO2,and an IrO2–ZrO2 solid solution.The IrO2–ZrO2 binary oxide coatings exhibited cracked structures with flat regions.A slight incorporation of ZrO2 promoted the crystallization of the active component IrO2.However,the crystallization of IrO2 was hindered when the added ZrO2 content was greater than 30at%.The appropriate incorporation of ZrO2 enhanced the electrocatalytic performance of the pure IrO2 coating.The Ti/70at%IrO2–30at%ZrO2 electrode,with its large active surface area,improved electrocatalytic activity,long service lifetime,and especially,lower cost,is the most effective for promoting oxygen evolution in sulfuric acid solution.展开更多
IrO2 and IrRuOx(Ir:Ru 60:40 at%),supported by 50 wt%onto titania nanotubes(TNTs)and(3 at%Nb)Nb-doped titania nanotubes(Nb-TNTs),as electrocatalysts for the oxygen evolution reaction(OER),were synthesized and character...IrO2 and IrRuOx(Ir:Ru 60:40 at%),supported by 50 wt%onto titania nanotubes(TNTs)and(3 at%Nb)Nb-doped titania nanotubes(Nb-TNTs),as electrocatalysts for the oxygen evolution reaction(OER),were synthesized and characterized by means of structural,surface analytical and electrochemical techniques.Nb doping of titania significantly increased the surface area of the support from 145(TNTs)to 260 m2g-1(Nb-TNTs),which was significantly higher than those of the Nb-doped titania supports previously reported in the literature.The surface analytical techniques showed good dispersion of the catalysts onto the supports.The X-ray photoelectron spectroscopy analyses showed that Nb was mainly in the form of Nb(IV)species,the suitable form to behave as a donor introducing free electrons to the conduction band of titania.The redox transitions of the cyclic voltammograms,in agreement with the XPS results,were found to be reversible.Despite the supported materials presented bigger crystallite sizes than the unsupported ones,the total number of active sites of the former was also higher due to their better catalyst dispersion.Considering the outer and the total charges of the cyclic voltammograms in the range 0.1–1.4 V,stability and electrode potentials at given current densities,the preferred catalyst was Ir O2 supported on the Nb-TNTs.The electrode potentials corresponding to given current densities were between the smallest ones given in the literature despite the small oxide loading used in this work and its Nb doping,thus making the Nb-TNTs-supported IrO2 catalyst a promising candidate for the OER.The good dispersion of IrO2,high specific surface area of the Nb-doped supports,accessibility of the electroactive centers,increased stability due to Nb doping and electron donor properties of the Nb(IV)oxide species were considered the main reasons for its good performance.展开更多
Surface reconstruction of electrocatalysts has been widely witnessed during the electrochemical processes.Here,NiS_(2),NiSe_(2), and Se doped NiS_(2)(Se-NiS_(2)) are fabricated for oxygen evolution reaction(OER) throu...Surface reconstruction of electrocatalysts has been widely witnessed during the electrochemical processes.Here,NiS_(2),NiSe_(2), and Se doped NiS_(2)(Se-NiS_(2)) are fabricated for oxygen evolution reaction(OER) through a mild sulfuration and/or selenylation process of Ni(OH)_(2) supported on carbon cloth(CC).Through careful in-situ Raman spectroscopy and ex-situ X-ray photoelectron spectroscopy,surface reconstruction of NiS_(2),NiSe_(2),and Se-NiS_(2) during the OER process has been revealed.A potentialdependent study shows that Se-NiS_(2) undergoes surface evolution at lower potentials and requires the lowest potential for conversion to NiOOH as a highly OER-active species,accompanied by the leaching of SO_(4)^(2-) and SeO_(4)^(2-) that can again be adsorbed on the catalyst surface to enhance the catalytic activity.Density functional theory(DFT) calculations confirm that Se-NiS_(2) is more susceptible to surface oxidation through the OER process.Therefore,Se-NiS_(2) exhibits outstanding OER activity and stability in alkaline conditions,requiring an overpotential of 343 mV at a current density of 50 mA cm^(-2).A novel insight is provided by our work in understanding the surface reconstruction and electrocatalytic mechanism of Ni-based chalcogenides.展开更多
Water splitting is important to the conversion and storage of renewable energy,but slow kinetics of the oxygen evolution reaction(OER)greatly limits its utility.Here,under visible light illumination,the p-n WO_(3)/SnS...Water splitting is important to the conversion and storage of renewable energy,but slow kinetics of the oxygen evolution reaction(OER)greatly limits its utility.Here,under visible light illumination,the p-n WO_(3)/SnSe_(2)(WS)heterojunction significantly activates OER catalysis of CoFe-layered double hydroxide(CF)/carbon nanotubes(CNTs).Specifically,the catalyst achieves an overpotential of 224 mV at 10 mA cm^(-2)and a small Tafel slope of 47 mV dec^(-1),superior to RuO_(2)and most previously reported transition metal-based OER catalysts.The p-n WS heterojunction shows strong light absorption to produce photogenerated carriers.The photogenerated holes are trapped by CF to suppresses the charge recombination and facilitate charge transfer,which accelerates OER kinetics and boost the activity for the OER.This work highlights the possibility of using heterojunctions to activate OER catalysis and advances the design of energy-efficient catalysts for water oxidation systems using solar energy.展开更多
Herein, novel plasmonic Bi metal in situ deposited in reduced Ti O2 microspheres(Bi@R-Ti O2) are fabricated via a bimetallic MOF-derived synthesized strategy by adjusting the synthesizing temperature. Different charac...Herein, novel plasmonic Bi metal in situ deposited in reduced Ti O2 microspheres(Bi@R-Ti O2) are fabricated via a bimetallic MOF-derived synthesized strategy by adjusting the synthesizing temperature. Different characterization techniques, including XRD, SEM, TEM, XPS, DRS, PL, EIS, and photocurrent generation, are performed to investigate the structural and optical properties of the as-prepared samples. The results indicate that the Bi particles are generated inside and outside of reduced Ti O2 microspheres via the reduction of Ti4+ and Bi3+ by ethylene glycol. When the annealing temperature is controlled at 300 o C, the corresponding Bi@R-Ti O2-300 sample with an appropriate amount of Bi nanoparticles exhibits the highest full solar spectrum photocatalytic oxygen evolution activity(4728.709 μmol h–1 g–1), which is 5.9 and 9.5 times higher than that of pure Ti O2 and Bi-Ti bimetal organic frameworks(Bi-Ti-MOFs). Several reasons are suggested for the above results:(1) Bi metal behaves as an "electron acceptor" to accelerate the charge carrier transfer from Ti O2 to Bi;(2) The surface plasmon resonance effect of loaded metallic Bi particles can enhance the visible and NIR light absorption capacity;(3) The generation of Ti3+ further narrows the band gap of TiO2.展开更多
Ru@RuO2 core-shell nanorods were successfully synthesized by heat-treating Ru nanorods with air oxidation through an accurate control of the temperature and time. The structure, composition, dimension, and adsorption ...Ru@RuO2 core-shell nanorods were successfully synthesized by heat-treating Ru nanorods with air oxidation through an accurate control of the temperature and time. The structure, composition, dimension, and adsorption property of the core-shell nanorods were well characterized with XRD and TEM. The catalytic activity and stability were electrochemically evaluated with a rotating disk electrode, a rotating ring-disk electrode, and chronopotentiometric methods. The Ru@RuO2 nanorods reveal excellent bifunctional catalytic activity and robust stability for both oxygen evolution reaction(OER) and hydrogen evolution reaction(HER). The overpotentials for OER and HER are 320 m V and 137 m V at the current density of10 m A cm-2, respectively. The catalytic activity of Ru@RuO2 nanorods for OER is 6.5 times higher than that of the state-of-the-art catalyst IrO2 according to the catalytic current density measured at 1.60 V(versus RHE).The catalytic activity of Ru@RuO2 nanorods for HER is comparable to 40%Pt/C by comparing the catalytic current densities at à0.2 V.展开更多
P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phas...P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phases remains a necessity.Herein,we design a P2/O3-type Na_(0.76)Ni_(0.31)Zn_(0.07)Mn_(0.50)Ti_(0.12)0_(2)(NNZMT)with high chemical/electrochemical stability by enhancing the coupling between the two phases.For the first time,a unique Na*extraction is observed from a Na-rich O3 phase by a Na-poor P2 phase and systematically investigated.This process is facilitated by Zn^(2+)/Ti^(4+)dual doping and calcination condition regulation,allowing a higher Na*content in the P2 phase with larger Na^(+)transport channels and enhancing Na transport kinetics.Because of reduced Na^(+)in the O3 phase,which increases the difficulty of H^(+)/Na^(+) exchange,the hydrostability of the O3 phase in NNZMT is considerably improved.Furthermore,Zn^(2+)/Ti^(4+)presence in NNZMT synergistically regulates oxygen redox chemistry,which effectively suppresses O_(2)/CO_(2) gas release and electrolyte decomposition,and completely inhibits phase transitions above 4.0 V.As a result,NNZMT achieves a high discharge capacity of 144.8 mA h g^(-1) with a median voltage of 3.42 V at 20 mA g^(-1) and exhibits excellent cycling performance with a capacity retention of 77.3% for 1000 cycles at 2000 mA g^(-1).This study provides an effective strategy and new insights into the design of high-performance layered-oxide cathode materials with enhanced structure/interface stability forSIBs.展开更多
A spinel oxide NiCo204 prepared by thermal decomposition is of very high activity for the oxygen evolution reaction(OER)in alkaline solution.The oxygen evolution overpotential on NiCo204 is 0.252-0.262V in 10 M NaOH s...A spinel oxide NiCo204 prepared by thermal decomposition is of very high activity for the oxygen evolution reaction(OER)in alkaline solution.The oxygen evolution overpotential on NiCo204 is 0.252-0.262V in 10 M NaOH solution at 343K and current density 100 mAcm^(-2).展开更多
Co3O4/SiO2 catalysts for CO oxidation were prepared by conventional incipient wetness impregnation followed by calcination at various temperatures. Their structures were char- acterized with X-ray diffraction (XRD),...Co3O4/SiO2 catalysts for CO oxidation were prepared by conventional incipient wetness impregnation followed by calcination at various temperatures. Their structures were char- acterized with X-ray diffraction (XRD), laser Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction (TPR) and X-ray absorption fine structure (XAFS) spectroscopy. Both XRD and Raman spectroscopy only detect the existence of Co3O4 crystallites in all catalysts. However, XPS results indicate that excess Co2+ ions are present on the surface of Co3O4 in Co3O4(200)/Si02 as compared with bulk Co3O4. Meanwhile, TPR results suggest the presence of surface oxygen vacancies on Co3O4 in Co3O4(200)/SiO2, and XAFS results demonstrate that Co3O4 in Co3O4(200)/SIO2 contains excess Co2+. Increasing calcination temperature results in oxidation of excess Co2+ and the decrease of the concentration of surface oxygen vacancies, consequently the for- mation of stoichiometric Co3O4 on supported catalysts. Among all Co3O4/SiO2 catalysts, Co3O4(200)/SiO2 exhibits the best catalytic performance towards CO oxidation, demonstrating that excess Co2+ and surface oxygen vacancies can enhance the catalytic activity of Co3O4 towards CO oxidation. These results nicely demonstrate the effect of calcination temperature on the structure and catalytic performance towards CO oxidation of silicasupported Co3O4 catalysts and highlight the important role of surface oxygen vacancies on Co3O4.展开更多
TiO2 nanosheets mainly exposed (001) facet were prepared through a hydrothermal process with HF as the morphology-directing agent. Ru and RuO2 species were loaded by photo-deposition methods to prepare the photocata...TiO2 nanosheets mainly exposed (001) facet were prepared through a hydrothermal process with HF as the morphology-directing agent. Ru and RuO2 species were loaded by photo-deposition methods to prepare the photocatalysts. The structural features of the catalysts were characterized by X-ray di raction, transmission electron microscopy, inductively cou-pled plasma atomic emission spectrum, and H2 Temperature-programmed reduction. The photocatalytic property was studied by the O2 evolution from water oxidation, which was examined with respect to the in uences of Ru contents as well as the oxidation and reduction treatments, suggesting the charge separation effect of the Ru species co-catalysts on di erent facets of TiO2 nanosheets. In contrast to Ru/TiO2 and RuO2/TiO2 with the single deposited co-catalyst, the optimized catalyst 0.5%Ru-1.0%RuO2/TiO2 with dual co-catalysts achieved a much improved catalytic performance, in terms of the synergetic effect of dual co-catalysts and the enhanced charge separation effect.展开更多
The development of efficient oxygen evolution electrocatalysts with reduced noble metal uses is a critical challenge for the deployment of various advanced energy conversion technologies.Here,a series of lanthanide-co...The development of efficient oxygen evolution electrocatalysts with reduced noble metal uses is a critical challenge for the deployment of various advanced energy conversion technologies.Here,a series of lanthanide-contained 6H-perovskites with a formula of Ba3LnIr2〇9(Ln=lanthanides)are investigated as oxygen evolution electrocatalysts,whose active subunits(i.e.,face-sharing Ir〇6 dimers)can be regulated by the lanthanides in terms of catalytic activity.By using density functional theory(DFT)calculations,we establish the theoretical trend in activity for Ba3LnIr2〇96H-perovskites,the activity of which is correlated with the difference of adsorption free energy(△G〇-△Goh)between O*and OH*reaction intermediates.We further establish a volcano curve between△Go—△Goh and the calculated 0 p-band center Among the Ba3LnIr2〇96H-perovskites,Ba3Lalr2〇9 locates at the peak of volcano curve,and correspondingly is the most active electrocatalyst due to the optimal 0 p-band property.展开更多
K2Ti6O13 whiskers were synthesized by conventional sol-gel method, sono-chemical assisted and microwave assisted sol-gel method in order to obtain catalysts with different particle sizes and to modify their optical, t...K2Ti6O13 whiskers were synthesized by conventional sol-gel method, sono-chemical assisted and microwave assisted sol-gel method in order to obtain catalysts with different particle sizes and to modify their optical, textural and electrochemical properties. These modifications improved their photocatalytic activity for H2 evolution and CO2 photo-reduction. Long K2Ti6O13 whiskers prepared by ultrasound assisted sol-gel method are the most active photocatalysts for the hydrogen evolution reaction using pure water as reactant (U-SG, 10,065 μmol g^-1). In contrast, an opposite behavior was observed using a mixture of ethanol-water, where the highest activity was achieved by the shortest and less crystalline K2Ti6O13 whiskers (C-SG, 3,2871 μmol g^-1). In case of CO2 photo-reduction, long whiskers that were also prepared by the sono-chemical assisted sol-gel method were the most active to transform CO2 to formaldehyde, methane, methanol and hydrogen. The EFB value of this catalyst is located very close to the potential for formaldehyde production and favors the selectivity to this organic product.展开更多
The most energy-inefficient step in the oxygen evolution reaction(OER), which involves a complicated four-electron transfer process, limits the efficiency of the electrochemical water splitting. Here, well-defined Ni/...The most energy-inefficient step in the oxygen evolution reaction(OER), which involves a complicated four-electron transfer process, limits the efficiency of the electrochemical water splitting. Here, well-defined Ni/Co3O4 nanoparticles coupled with N-doped carbon hybrids(Ni/Co3O4@NC) were synthesized via a facile impregnation-calcination method as efficient electrocatalysts for OER in alkaline media. Notably, the impregnation of the polymer with Ni and Co ions in the first step ensured the homogeneous distribution of metals, thus guaranteeing the subsequent in situ calcination reaction, which produced well-dispersed Ni and Co3O4 nanoparticles. Moreover, the N-doped carbon matrix formed at high temperatures could effectively prevent the aggregation and coalescence, and regulate the electronic configuration of active species. Benefiting from the synergistic effect between the Ni, Co3O4, and NC species, the obtained Ni/Co3O4@NC hybrids exhibited enhanced OER activities and remarkable stability in an alkaline solution with a smaller overpotential of 350 m V to afford 10 m A cm-2, lower Tafel slope of 52.27 m V dec-1, smaller charge-transfer resistance, and higher double-layer capacitance of 25.53 m F cm-2 compared to those of unary Co3O4@NC or Ni@NC metal hybrids. Therefore, this paper presents a facile strategy for designing other heteroatom-doped oxides coupled with ideal carbon materials as electrocatalysts for the OER.展开更多
Oxygen vacancies(Vo)in electrocatalysts are closely correlated with the hydrogen evo-lution reaction(HER)activity.The role of vacancy defects and the effect of their concentration,how-ever,yet remains unclear.Herein,B...Oxygen vacancies(Vo)in electrocatalysts are closely correlated with the hydrogen evo-lution reaction(HER)activity.The role of vacancy defects and the effect of their concentration,how-ever,yet remains unclear.Herein,Bi2O3,an unfavorable electrocata-lyst for the HER due to a less than ideal hydrogen adsorption Gibbs free energy(ΔGH*),is utilized as a perfect model to explore the func-tion of Vo on HER performance.Through a facile plasma irradia-tion strategy,Bi2O3 nanosheets with different Vo concentrations are fabricated to evaluate the influence of defects on the HER process.Unexpectedly,while the generated oxygen vacancies contribute to the enhanced HER performance,higher Vo concentrations beyond a saturation value result in a significant drop in HER activity.By tunning the Vo concentration in the Bi_(2)O_(3)nanosheets via adjusting the treatment time,the Bi2O3 catalyst with an optimized oxygen vacancy concentration and detectable charge carrier concentration of 1.52×10^(24)cm^(−3)demonstrates enhanced HER performance with an overpotential of 174.2 mV to reach 10 mA cm^(−2),a Tafel slope of 80 mV dec−1,and an exchange current density of 316 mA cm−2 in an alkaline solution,which approaches the top-tier activity among Bi-based HER electrocatalysts.Density-functional theory calculations confirm the preferred adsorption of H*onto Bi2O3 as a function of oxygen chemical potential(ΔμO)and oxygen partial potential(PO2)and reveal that high Vo concentrations result in excessive stability of adsorbed hydrogen and hence the inferior HER activity.This study reveals the oxygen vacancy concentration-HER catalytic activity relationship and provides insights into activating catalytically inert materials into highly efficient electrocatalysts.展开更多
Herein, Co_3O_4 nanoparticles/nitrogen-doped carbon(Co_3O_4/NPC) composites with different structures were prepared via a facile method. Structure control was achieved by the rational morphology design of ZIF-67 precu...Herein, Co_3O_4 nanoparticles/nitrogen-doped carbon(Co_3O_4/NPC) composites with different structures were prepared via a facile method. Structure control was achieved by the rational morphology design of ZIF-67 precursors, which were then pyrolyzed in air to obtain Co_3O_4/NPC composites. When applied as catalysts for the oxygen evolution reaction(OER), the M-Co_3O_4/NPC composites derived from the flower-like ZIF-67 showedsuperior catalytic activities than those derived from the rhombic dodecahedron and hollow spherical ZIF-67. The former M-Co_3O_4/NPC composite displayed a small overpotential of 0.3 V, low onset potential of 1.41 V, small Tafel slope of 83 m V dec^(-1), and a desirable stability.(94.7% OER activity was retained after 10 h.) The excellent performance of the flower-like M-Co_3O_4/NPC composite in the OER was attributed to its favorable structure.展开更多
基金financial support from the National Natural Science Foundation of China (52203070)the Open Fund of State Key Laboratory of New Textile Materials and Advanced Processing Technologies (FZ2022005)+2 种基金the Open Fund of Hubei Key Laboratory of Biomass Fiber and Ecological Dyeing and Finishing (STRZ202203)the financial support provided by the China Scholarship Council (CSC)Visiting Scholar Programfinancial support from Institute for Sustainability,Energy and Resources,The University of Adelaide,Future Making Fellowship,Australia。
文摘The incorporation of partial A-site substitution in perovskite oxides represents a promising strategy for precisely controlling the electronic configuration and enhancing its intrinsic catalytic activity.Conventional methods for A-site substitution typically involve prolonged high-temperature processes.While these processes promote the development of unique nanostructures with highly exposed active sites,they often result in the uncontrolled configuration of introduced elements.Herein,we present a novel approach for synthesizing two-dimensional(2D)porous GdFeO_(3) perovskite with A-site strontium(Sr)substitution utilizing microwave shock method.This technique enables precise control of the Sr content and simultaneous construction of 2D porous structures in one step,capitalizing on the advantages of rapid heating and cooling(temperature~1100 K,rate~70 K s^(-1)).The active sites of this oxygen-rich defect structure can be clearly revealed through the simulation of the electronic configuration and the comprehensive analysis of the crystal structure.For electrocatalytic oxygen evolution reaction application,the synthesized 2D porous Gd_(0.8)Sr_(0.2)FeO_(3) electrocatalyst exhibits an exceptional overpotential of 294 mV at a current density of 10 mA cm^(-2)and a small Tafel slope of 55.85 mV dec^(-1)in alkaline electrolytes.This study offers a fresh perspective on designing crystal configurations and the construction of nanostructures in perovskite.
基金Funded by the Doctoral Fund of Chengdu University(No.2081919131)the Sichuan Science and Technology Program(No.2023YFG0229)。
文摘Ni^(2+)/Cu^(2+)/SO_(4)^(2-)/polyvinyl alcohol precursor fibers with uniform diameters were prepared through electrospinning.Nickel-based composite nanoalloys containing Ni,Cu,and S were prepared through heat treatment in an Ar atmosphere.The experimental results show that the main components of the prepared nanoalloys are NiCu,Ni_(3)S_(2),Ni,and C.The nanoalloys exhibit fine grain sizes about 200-500 nm,which can increase with increasing heat treatment temperature.Electrochemical test results show that the nickel sulfidemodified NiCu nanoalloy composites exhibit excellent oxygen evolution reaction properties,and the oxygen evolution reaction properties gradually improve with the increasing heat treatment temperature.The sample prepared at 1 000℃ for 40 min show a low overpotential of 423 mV and a small Tafel slope of 134 mV·dec^(-1) at a current density of 10 mA·cm^(-2).
基金funding support from the National Natural Science Foundation of China(2200206852272222,and 52072197)+12 种基金the Taishan Scholar Young Talent Program(tsqn201909114)the Youth Innovation and Technology Foundation of Shandong Higher Education Institutions,China(2019KJC004)the Outstanding Youth Foundation of Shandong Province,China(ZR2019JQ14)the Major Basic Research Program of Natural Science Foundation of Shandong Province under Grant No.ZR2020ZD09Youth Innovation Team Development Program of Shandong Higher Education Institutions(2022KJ155)the Major Scientific and Technological Innovation Project(2019JZZY020405)the Shandong Province“Double-Hundred Talent Plan”(WST2020003)Project funded by the China Postdoctoral Science Foundation(2021M691700)the Natural Science Foundation of Shandong Province of China(ZR2019BB002ZR2018BB031)the Postdoctoral Innovation Project of Shandong Province(SDCXZG-202203021)the Scientific and Technological Innovation Promotion Project for Small-medium Enterprises of Shandong Province(2022TSGC1257)the Major Research Program of Jining City(2020ZDZP024)。
文摘Constructing highly-efficient electrocatalysts toward hydrogen evolution reaction(HER)/oxygen evolution reaction(OER)/oxygen reduction reaction(ORR)with excellent stability is quite important for the development of renewable energy-related applications.Herein,Co-Ru based compounds supported on nitrogen doped two-dimensional(2D)carbon nanosheets(NCN)are developed via one step pyrolysis procedure(Co-Ru/NCN)for HER/ORR and following low-temperature oxidation process(Co-Ru@RuO_(x)/NCN)for OER.The specific 2D morphology guarantees abundant active sites exposure.Furthermore,the synergistic effects arising from the interaction between Co and Ru are crucial in enhancing the catalytic performance.Thus,the resulting Co-Ru/NCN shows remarkable electrocatalytic performance for HER(70 mV at 10 mA cm^(-2))in 1 M KOH and ORR(half-wave potential E_(1/2)=0.81 V)in 0.1 M KOH.Especially,the Co-Ru@RuO_(x)/NCN obtained by oxidation exhibits splendid OER performance in both acid(230 mV at 10 mA cm^(-2))and alkaline media(270 mV at 10 mA cm^(-2))coupled with excellent stability.Consequently,the fabricated two-electrode water-splitting device exhibits excellent performance in both acidic and alkaline environments.This research provides a promising avenue for the advancement of multifunctional nanomaterials.
基金supported by the Fundamental Research Funds for the Central Universities(DUT21LK34)Natural Science Foundation of Liaoning Province(2020-MS-113).
文摘Rational design of oxygen evolution reaction(OER)catalysts at low cost would greatly benefit the economy.Taking advantage of earth-abundant elements Si,Co and Ni,we produce a unique-structure where cobalt-nickel silicate hydroxide[Co_(2.5)Ni_(0.5)Si_(2)O_(5)(OH)_(4)]is vertically grown on a reduced graphene oxide(rGO)support(CNS@rGO).This is developed as a low-cost and prospective OER catalyst.Compared to cobalt or nickel silicate hydroxide@rGO(CS@rGO and NS@rGO,respectively)nanoarrays,the bimetal CNS@rGO nanoarray exhibits impressive OER performance with an overpotential of 307 mV@10 mA cm^(-2).This value is higher than that of CS@rGO and NS@rGO.The CNS@rGO nanoarray has an overpotential of 446 mV@100 mA cm^(-2),about 1.4 times that of the commercial RuO_(2)electrocatalyst.The achieved OER activity is superior to the state-of-the-art metal oxides/hydroxides and their derivatives.The vertically grown nanostructure and optimized metal-support electronic interactions play an indispensable role for OER performance improvement,including a fast electron transfer pathway,short proton/electron diffusion distance,more active metal centers,as well as optimized dualatomic electron density.Taking advantage of interlay chemical regulation and the in-situ growth method,the advanced-structural CNS@rGO nanoarrays provide a new horizon to the rational and flexible design of efficient and promising OER electrocatalysts.
基金Supported by the National Natural Science Foundation of China (20406019).
文摘F-PbO2 electrode and polytetrafluoroethylene (PTFE) doped F-PbO2 electrode (PTFE-F-PbO2) were prepared on a plexiglas sheet substrate by a series of procedure including chemical and electrochemical depositions. The electrochemical activities of these two electrodes for oxygen evolution (OE) reaction were examined by electrochemical tests. In comparison with F-PbO2, PTFE-F-PbO2 electrode exhibited larger active surface area and higher oxygen vacancy deficiency, which resulted in its higher electrocatalytic activity for OE. In addition, both exchange current density and activation energy of the electrodes for OE were calculated in terms of active surface area. The values of exchange current density and activation energy in 0.5 mol·L^-1 H2SO4 aqueous solution were 1.125×10^ -3 mA·cm^-2 and 18.62 kJ·mol^-1 for PTFE-F-PbO2, and 8.384×10^-4 mA·cm^- 2 and 28.98 kJ·mol^-1 for F-PbO2, respectively. Because these values are calculated on the basis of the active surface areas of the electrodes, the enhanced activity of PTFE-F-PbO2 can be attributed to an increase in oxygen vacancy deficiency of PbO2 due to doping by PTFE. The influence of PTFE adulteration on the activity of PbO2 film electrode for OE was investigated in detail in this study.
基金financially supported by the National Natural Science Foundation of China (Nos. U1802253, 51974025 and 51674026)the Guangxi Innovation-Driven Development Project (No. AA18242042-1)+1 种基金the Beijing Natural Science Foundation of China (No. 2182040)the Fundamental Research Funds for the Central Universities (FRF22TT-19-001)
文摘In this study,we prepared Ti/IrO2–ZrO2 electrodes with different ZrO2 contents using zirconium-n-butoxide(C16H36O4Zr)and chloroiridic acid(H2IrCl6)via a sol–gel route.To explore the effect of ZrO2 content on the surface properties and electrochemical behavior of electrodes,we performed physical characterizations and electrochemical measurements.The obtained results revealed that the binary oxide coating was composed of rutile IrO2,amorphous ZrO2,and an IrO2–ZrO2 solid solution.The IrO2–ZrO2 binary oxide coatings exhibited cracked structures with flat regions.A slight incorporation of ZrO2 promoted the crystallization of the active component IrO2.However,the crystallization of IrO2 was hindered when the added ZrO2 content was greater than 30at%.The appropriate incorporation of ZrO2 enhanced the electrocatalytic performance of the pure IrO2 coating.The Ti/70at%IrO2–30at%ZrO2 electrode,with its large active surface area,improved electrocatalytic activity,long service lifetime,and especially,lower cost,is the most effective for promoting oxygen evolution in sulfuric acid solution.
文摘IrO2 and IrRuOx(Ir:Ru 60:40 at%),supported by 50 wt%onto titania nanotubes(TNTs)and(3 at%Nb)Nb-doped titania nanotubes(Nb-TNTs),as electrocatalysts for the oxygen evolution reaction(OER),were synthesized and characterized by means of structural,surface analytical and electrochemical techniques.Nb doping of titania significantly increased the surface area of the support from 145(TNTs)to 260 m2g-1(Nb-TNTs),which was significantly higher than those of the Nb-doped titania supports previously reported in the literature.The surface analytical techniques showed good dispersion of the catalysts onto the supports.The X-ray photoelectron spectroscopy analyses showed that Nb was mainly in the form of Nb(IV)species,the suitable form to behave as a donor introducing free electrons to the conduction band of titania.The redox transitions of the cyclic voltammograms,in agreement with the XPS results,were found to be reversible.Despite the supported materials presented bigger crystallite sizes than the unsupported ones,the total number of active sites of the former was also higher due to their better catalyst dispersion.Considering the outer and the total charges of the cyclic voltammograms in the range 0.1–1.4 V,stability and electrode potentials at given current densities,the preferred catalyst was Ir O2 supported on the Nb-TNTs.The electrode potentials corresponding to given current densities were between the smallest ones given in the literature despite the small oxide loading used in this work and its Nb doping,thus making the Nb-TNTs-supported IrO2 catalyst a promising candidate for the OER.The good dispersion of IrO2,high specific surface area of the Nb-doped supports,accessibility of the electroactive centers,increased stability due to Nb doping and electron donor properties of the Nb(IV)oxide species were considered the main reasons for its good performance.
基金supported by the financial support from the National Natural Science Foundation of China (21871065, 22071038, 22209129)the Heilongjiang Touyan Team (HITTY20190033)the Interdisciplinary Research Foundation of HIT (IR2021205)。
文摘Surface reconstruction of electrocatalysts has been widely witnessed during the electrochemical processes.Here,NiS_(2),NiSe_(2), and Se doped NiS_(2)(Se-NiS_(2)) are fabricated for oxygen evolution reaction(OER) through a mild sulfuration and/or selenylation process of Ni(OH)_(2) supported on carbon cloth(CC).Through careful in-situ Raman spectroscopy and ex-situ X-ray photoelectron spectroscopy,surface reconstruction of NiS_(2),NiSe_(2),and Se-NiS_(2) during the OER process has been revealed.A potentialdependent study shows that Se-NiS_(2) undergoes surface evolution at lower potentials and requires the lowest potential for conversion to NiOOH as a highly OER-active species,accompanied by the leaching of SO_(4)^(2-) and SeO_(4)^(2-) that can again be adsorbed on the catalyst surface to enhance the catalytic activity.Density functional theory(DFT) calculations confirm that Se-NiS_(2) is more susceptible to surface oxidation through the OER process.Therefore,Se-NiS_(2) exhibits outstanding OER activity and stability in alkaline conditions,requiring an overpotential of 343 mV at a current density of 50 mA cm^(-2).A novel insight is provided by our work in understanding the surface reconstruction and electrocatalytic mechanism of Ni-based chalcogenides.
基金the National Natural Science Foundation of China(No.41807213)the Hydrogeo-logical Survey Project of Huangshui River(No.DD20190331).
文摘Water splitting is important to the conversion and storage of renewable energy,but slow kinetics of the oxygen evolution reaction(OER)greatly limits its utility.Here,under visible light illumination,the p-n WO_(3)/SnSe_(2)(WS)heterojunction significantly activates OER catalysis of CoFe-layered double hydroxide(CF)/carbon nanotubes(CNTs).Specifically,the catalyst achieves an overpotential of 224 mV at 10 mA cm^(-2)and a small Tafel slope of 47 mV dec^(-1),superior to RuO_(2)and most previously reported transition metal-based OER catalysts.The p-n WS heterojunction shows strong light absorption to produce photogenerated carriers.The photogenerated holes are trapped by CF to suppresses the charge recombination and facilitate charge transfer,which accelerates OER kinetics and boost the activity for the OER.This work highlights the possibility of using heterojunctions to activate OER catalysis and advances the design of energy-efficient catalysts for water oxidation systems using solar energy.
基金the National Natural Science Foundation of China(51872173 and 51772176)Taishan Scholarship of Young Scholars(tsqn201812068)+2 种基金Natural Science Foundation of Shandong Province(ZR2017JL020)Taishan Scholarship of Climbing Plan(tspd20161006)Key Research and Development Program of Shandong Province(2018GGX102028)~~
文摘Herein, novel plasmonic Bi metal in situ deposited in reduced Ti O2 microspheres(Bi@R-Ti O2) are fabricated via a bimetallic MOF-derived synthesized strategy by adjusting the synthesizing temperature. Different characterization techniques, including XRD, SEM, TEM, XPS, DRS, PL, EIS, and photocurrent generation, are performed to investigate the structural and optical properties of the as-prepared samples. The results indicate that the Bi particles are generated inside and outside of reduced Ti O2 microspheres via the reduction of Ti4+ and Bi3+ by ethylene glycol. When the annealing temperature is controlled at 300 o C, the corresponding Bi@R-Ti O2-300 sample with an appropriate amount of Bi nanoparticles exhibits the highest full solar spectrum photocatalytic oxygen evolution activity(4728.709 μmol h–1 g–1), which is 5.9 and 9.5 times higher than that of pure Ti O2 and Bi-Ti bimetal organic frameworks(Bi-Ti-MOFs). Several reasons are suggested for the above results:(1) Bi metal behaves as an "electron acceptor" to accelerate the charge carrier transfer from Ti O2 to Bi;(2) The surface plasmon resonance effect of loaded metallic Bi particles can enhance the visible and NIR light absorption capacity;(3) The generation of Ti3+ further narrows the band gap of TiO2.
基金the U.S.Department of the ArmyU.S.Army Materiel Command for supporting this work
文摘Ru@RuO2 core-shell nanorods were successfully synthesized by heat-treating Ru nanorods with air oxidation through an accurate control of the temperature and time. The structure, composition, dimension, and adsorption property of the core-shell nanorods were well characterized with XRD and TEM. The catalytic activity and stability were electrochemically evaluated with a rotating disk electrode, a rotating ring-disk electrode, and chronopotentiometric methods. The Ru@RuO2 nanorods reveal excellent bifunctional catalytic activity and robust stability for both oxygen evolution reaction(OER) and hydrogen evolution reaction(HER). The overpotentials for OER and HER are 320 m V and 137 m V at the current density of10 m A cm-2, respectively. The catalytic activity of Ru@RuO2 nanorods for OER is 6.5 times higher than that of the state-of-the-art catalyst IrO2 according to the catalytic current density measured at 1.60 V(versus RHE).The catalytic activity of Ru@RuO2 nanorods for HER is comparable to 40%Pt/C by comparing the catalytic current densities at à0.2 V.
基金supported by the National Natural Science Foundation of China (22169002)the Chongzuo Key Research and Development Program of China (20220603)the Counterpart Aid Project for Discipline Construction from Guangxi University(2023M02)
文摘P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phases remains a necessity.Herein,we design a P2/O3-type Na_(0.76)Ni_(0.31)Zn_(0.07)Mn_(0.50)Ti_(0.12)0_(2)(NNZMT)with high chemical/electrochemical stability by enhancing the coupling between the two phases.For the first time,a unique Na*extraction is observed from a Na-rich O3 phase by a Na-poor P2 phase and systematically investigated.This process is facilitated by Zn^(2+)/Ti^(4+)dual doping and calcination condition regulation,allowing a higher Na*content in the P2 phase with larger Na^(+)transport channels and enhancing Na transport kinetics.Because of reduced Na^(+)in the O3 phase,which increases the difficulty of H^(+)/Na^(+) exchange,the hydrostability of the O3 phase in NNZMT is considerably improved.Furthermore,Zn^(2+)/Ti^(4+)presence in NNZMT synergistically regulates oxygen redox chemistry,which effectively suppresses O_(2)/CO_(2) gas release and electrolyte decomposition,and completely inhibits phase transitions above 4.0 V.As a result,NNZMT achieves a high discharge capacity of 144.8 mA h g^(-1) with a median voltage of 3.42 V at 20 mA g^(-1) and exhibits excellent cycling performance with a capacity retention of 77.3% for 1000 cycles at 2000 mA g^(-1).This study provides an effective strategy and new insights into the design of high-performance layered-oxide cathode materials with enhanced structure/interface stability forSIBs.
文摘A spinel oxide NiCo204 prepared by thermal decomposition is of very high activity for the oxygen evolution reaction(OER)in alkaline solution.The oxygen evolution overpotential on NiCo204 is 0.252-0.262V in 10 M NaOH solution at 343K and current density 100 mAcm^(-2).
文摘Co3O4/SiO2 catalysts for CO oxidation were prepared by conventional incipient wetness impregnation followed by calcination at various temperatures. Their structures were char- acterized with X-ray diffraction (XRD), laser Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction (TPR) and X-ray absorption fine structure (XAFS) spectroscopy. Both XRD and Raman spectroscopy only detect the existence of Co3O4 crystallites in all catalysts. However, XPS results indicate that excess Co2+ ions are present on the surface of Co3O4 in Co3O4(200)/Si02 as compared with bulk Co3O4. Meanwhile, TPR results suggest the presence of surface oxygen vacancies on Co3O4 in Co3O4(200)/SiO2, and XAFS results demonstrate that Co3O4 in Co3O4(200)/SIO2 contains excess Co2+. Increasing calcination temperature results in oxidation of excess Co2+ and the decrease of the concentration of surface oxygen vacancies, consequently the for- mation of stoichiometric Co3O4 on supported catalysts. Among all Co3O4/SiO2 catalysts, Co3O4(200)/SiO2 exhibits the best catalytic performance towards CO oxidation, demonstrating that excess Co2+ and surface oxygen vacancies can enhance the catalytic activity of Co3O4 towards CO oxidation. These results nicely demonstrate the effect of calcination temperature on the structure and catalytic performance towards CO oxidation of silicasupported Co3O4 catalysts and highlight the important role of surface oxygen vacancies on Co3O4.
文摘TiO2 nanosheets mainly exposed (001) facet were prepared through a hydrothermal process with HF as the morphology-directing agent. Ru and RuO2 species were loaded by photo-deposition methods to prepare the photocatalysts. The structural features of the catalysts were characterized by X-ray di raction, transmission electron microscopy, inductively cou-pled plasma atomic emission spectrum, and H2 Temperature-programmed reduction. The photocatalytic property was studied by the O2 evolution from water oxidation, which was examined with respect to the in uences of Ru contents as well as the oxidation and reduction treatments, suggesting the charge separation effect of the Ru species co-catalysts on di erent facets of TiO2 nanosheets. In contrast to Ru/TiO2 and RuO2/TiO2 with the single deposited co-catalyst, the optimized catalyst 0.5%Ru-1.0%RuO2/TiO2 with dual co-catalysts achieved a much improved catalytic performance, in terms of the synergetic effect of dual co-catalysts and the enhanced charge separation effect.
文摘The development of efficient oxygen evolution electrocatalysts with reduced noble metal uses is a critical challenge for the deployment of various advanced energy conversion technologies.Here,a series of lanthanide-contained 6H-perovskites with a formula of Ba3LnIr2〇9(Ln=lanthanides)are investigated as oxygen evolution electrocatalysts,whose active subunits(i.e.,face-sharing Ir〇6 dimers)can be regulated by the lanthanides in terms of catalytic activity.By using density functional theory(DFT)calculations,we establish the theoretical trend in activity for Ba3LnIr2〇96H-perovskites,the activity of which is correlated with the difference of adsorption free energy(△G〇-△Goh)between O*and OH*reaction intermediates.We further establish a volcano curve between△Go—△Goh and the calculated 0 p-band center Among the Ba3LnIr2〇96H-perovskites,Ba3Lalr2〇9 locates at the peak of volcano curve,and correspondingly is the most active electrocatalyst due to the optimal 0 p-band property.
基金CONACYT (CB-2014-237049, PDCPN-2015-487 and Ph. D. scholarship 635249) for the financial support
文摘K2Ti6O13 whiskers were synthesized by conventional sol-gel method, sono-chemical assisted and microwave assisted sol-gel method in order to obtain catalysts with different particle sizes and to modify their optical, textural and electrochemical properties. These modifications improved their photocatalytic activity for H2 evolution and CO2 photo-reduction. Long K2Ti6O13 whiskers prepared by ultrasound assisted sol-gel method are the most active photocatalysts for the hydrogen evolution reaction using pure water as reactant (U-SG, 10,065 μmol g^-1). In contrast, an opposite behavior was observed using a mixture of ethanol-water, where the highest activity was achieved by the shortest and less crystalline K2Ti6O13 whiskers (C-SG, 3,2871 μmol g^-1). In case of CO2 photo-reduction, long whiskers that were also prepared by the sono-chemical assisted sol-gel method were the most active to transform CO2 to formaldehyde, methane, methanol and hydrogen. The EFB value of this catalyst is located very close to the potential for formaldehyde production and favors the selectivity to this organic product.
文摘The most energy-inefficient step in the oxygen evolution reaction(OER), which involves a complicated four-electron transfer process, limits the efficiency of the electrochemical water splitting. Here, well-defined Ni/Co3O4 nanoparticles coupled with N-doped carbon hybrids(Ni/Co3O4@NC) were synthesized via a facile impregnation-calcination method as efficient electrocatalysts for OER in alkaline media. Notably, the impregnation of the polymer with Ni and Co ions in the first step ensured the homogeneous distribution of metals, thus guaranteeing the subsequent in situ calcination reaction, which produced well-dispersed Ni and Co3O4 nanoparticles. Moreover, the N-doped carbon matrix formed at high temperatures could effectively prevent the aggregation and coalescence, and regulate the electronic configuration of active species. Benefiting from the synergistic effect between the Ni, Co3O4, and NC species, the obtained Ni/Co3O4@NC hybrids exhibited enhanced OER activities and remarkable stability in an alkaline solution with a smaller overpotential of 350 m V to afford 10 m A cm-2, lower Tafel slope of 52.27 m V dec-1, smaller charge-transfer resistance, and higher double-layer capacitance of 25.53 m F cm-2 compared to those of unary Co3O4@NC or Ni@NC metal hybrids. Therefore, this paper presents a facile strategy for designing other heteroatom-doped oxides coupled with ideal carbon materials as electrocatalysts for the OER.
基金This work was financially supported by the Australian Research Council(ARC)through Future Fellowship grants(FT180100387 and FT160100281)Discovery Projects(DP200103568,DP210100472,and DP200102546)+1 种基金WL thanks the support of the Science and Technology Commission of Shanghai Municipality(19520713200)Open access funding provided by Shanghai Jiao Tong University
文摘Oxygen vacancies(Vo)in electrocatalysts are closely correlated with the hydrogen evo-lution reaction(HER)activity.The role of vacancy defects and the effect of their concentration,how-ever,yet remains unclear.Herein,Bi2O3,an unfavorable electrocata-lyst for the HER due to a less than ideal hydrogen adsorption Gibbs free energy(ΔGH*),is utilized as a perfect model to explore the func-tion of Vo on HER performance.Through a facile plasma irradia-tion strategy,Bi2O3 nanosheets with different Vo concentrations are fabricated to evaluate the influence of defects on the HER process.Unexpectedly,while the generated oxygen vacancies contribute to the enhanced HER performance,higher Vo concentrations beyond a saturation value result in a significant drop in HER activity.By tunning the Vo concentration in the Bi_(2)O_(3)nanosheets via adjusting the treatment time,the Bi2O3 catalyst with an optimized oxygen vacancy concentration and detectable charge carrier concentration of 1.52×10^(24)cm^(−3)demonstrates enhanced HER performance with an overpotential of 174.2 mV to reach 10 mA cm^(−2),a Tafel slope of 80 mV dec−1,and an exchange current density of 316 mA cm−2 in an alkaline solution,which approaches the top-tier activity among Bi-based HER electrocatalysts.Density-functional theory calculations confirm the preferred adsorption of H*onto Bi2O3 as a function of oxygen chemical potential(ΔμO)and oxygen partial potential(PO2)and reveal that high Vo concentrations result in excessive stability of adsorbed hydrogen and hence the inferior HER activity.This study reveals the oxygen vacancy concentration-HER catalytic activity relationship and provides insights into activating catalytically inert materials into highly efficient electrocatalysts.
基金supported by the Scientific and Technological Innovation Platform of Fujian Province(2006L2003)Scientific Research Project of Wuyi University(YJ201706)
文摘Herein, Co_3O_4 nanoparticles/nitrogen-doped carbon(Co_3O_4/NPC) composites with different structures were prepared via a facile method. Structure control was achieved by the rational morphology design of ZIF-67 precursors, which were then pyrolyzed in air to obtain Co_3O_4/NPC composites. When applied as catalysts for the oxygen evolution reaction(OER), the M-Co_3O_4/NPC composites derived from the flower-like ZIF-67 showedsuperior catalytic activities than those derived from the rhombic dodecahedron and hollow spherical ZIF-67. The former M-Co_3O_4/NPC composite displayed a small overpotential of 0.3 V, low onset potential of 1.41 V, small Tafel slope of 83 m V dec^(-1), and a desirable stability.(94.7% OER activity was retained after 10 h.) The excellent performance of the flower-like M-Co_3O_4/NPC composite in the OER was attributed to its favorable structure.