Water-splitting reactions such as the hydrogen evolution reaction(HER)and the oxygen evolution reaction(OER)typically require expensive noble metal-based electrocatalysts.This has motivated researchers to develop nove...Water-splitting reactions such as the hydrogen evolution reaction(HER)and the oxygen evolution reaction(OER)typically require expensive noble metal-based electrocatalysts.This has motivated researchers to develop novel,cost-effective electrocatalytic systems.In this study,a new multicomponent nanocomposite was assembled by combining functionalized multiwalled carbon nanotubes,a Cu-based metal–organic framework(MOF)(HKUST-1 or HK),and a sulfidized NiMn-layered double hydroxide(NiMn-S).The resulting nanocomposite,abbreviated as MW/HK/NiMn-S,features a unique architecture,high porosity,numerous electroactive Cu/Ni/Mn sites,fast charge transfer,excellent structural stability,and conductivity.At a current density of 10 mA cm-2,this dual-function electrocatalyst shows remarkable performance,with ultralow overpotential values of 163 mV(OER)or 73 mV(HER),as well as low Tafel slopes(57 and 75 mV dec-1,respectively).Additionally,its high turnover frequency values(4.43 s-1 for OER;3.96 s-1 for HER)are significantly superior to those of standard noble metal-based Pt/C and IrO2 systems.The synergistic effect of the nanocomposite's different components is responsible for its enhanced electrocatalytic performance.A density functional theory study revealed that the multi-interface and multicomponent heterostructure contribute to increased electrical conductivity and decreased energy barrier,resulting in superior electrocatalytic HER/OER activity.This study presents a novel vision for designing advanced electrocatalysts with superior performance in water splitting.Various composites have been utilized in water-splitting applications.This study investigates the use of the MW/HK/NiMn-S electrocatalyst for water splitting for the first time to indicate the synergistic effect between carbon-based materials along with layered double hydroxide compounds and porous compounds of MOF.The unique features of each component in this composite can be an interesting topic in the field of water splitting.展开更多
Improving catalytic activity and durabilty through the structural and compositional development of bifunctional electrocatalysts with low cost,high activity and stability is a challenging issue in electrochemical wate...Improving catalytic activity and durabilty through the structural and compositional development of bifunctional electrocatalysts with low cost,high activity and stability is a challenging issue in electrochemical water splitting.Herein,we report the fabrication of heterostructured P-CoMoO_(4)@NiCoP on a Ni foam substrate through interface engineering,by adjusting its composition and architecture.Benefitting from the tailored electronic structure and exposed active sites,the heterostructured P-CoMoO_(4)@NiCoP/NF arrays can be coordinated to boost the overall water splitting.In addition,the superhydrophilic and superaerophobic properties of P-CoMoO_(4)@NiCoP/NF make it conducive to water dissociation and bubble separation in the electrocatalytic process.The heterostructured PCoMoO_(4)@NiCoP/NF exhibits excellent bifunctional electrocatalysis activity with a low overpotential of 66 mV at 10 mA cm^(-2) for HER and 252 mV at 100 mA cm^(-2) for OER.Only 1.62 V potential is required to deliver 20 mA cm^(-2) in a two-electrode electrolysis system,providing a decent overall water splitting performance.The rational construction of the heterostructure makes it possible to regulate the electronic structures and active sites of the electrocatalysts to promote their catalytic activity.展开更多
Transition-metal phosphides(TMPs)with high catalytic activity are widely used in the design of electrodes for water splitting.However,a major challenge is how to achieve the trade-off between activity and stability of...Transition-metal phosphides(TMPs)with high catalytic activity are widely used in the design of electrodes for water splitting.However,a major challenge is how to achieve the trade-off between activity and stability of TMPs.Herein,a novel method for synthesizing CoP nanoparticles encapsu-lated in a rich-defect carbon shell(CoP/DCS)is developed through the self-assembly of modified polycyclic aromatic molecules.The graft and removal of high-activity C-N bonds of aromatic molecules render the controllable design of crystallite defects of carbon shell.The density functional theory calculation indicates that the carbon defects with unpaired electrons could effectively tailor the band structure of CoP.Benefiting from the improved activity and corrosion resistance,the CoP/DCS delivers outstanding difunctional hydrogen evolution reaction(88 mV)and oxygen evolution reaction(251 mV)performances at 10 mA cm^(−2)current density.Furthermore,the coupled water electrolyzer with CoP/DCS as both the cathode and anode presents ultralow cell voltages of 1.49 V to achieve 10 mA cm^(−2)with long-time stability.This strategy to improve TMPs electrocatalyst with rich-DCS and heterogeneous structure will inspire the design of other transition metal compound electrocatalysts for water splitting.展开更多
The inefficiency of water splitting is mainly due to the sluggish anodic water oxidation reaction. Replacing water oxidation with thermodynamically more favorable selective methanol oxidation reaction and developing r...The inefficiency of water splitting is mainly due to the sluggish anodic water oxidation reaction. Replacing water oxidation with thermodynamically more favorable selective methanol oxidation reaction and developing robust bifunctional electrocatalysts are of great significance. Herein, a hierarchical heteronanostructure with Ni–Co layered double hydroxide(LDH) ultrathin nanosheets coated on cobalt phosphide nanosheets arrays(CoxP@NiCo-LDH) are fabricated and used for co-electrolysis of methanol/water to co-produce value-added formate and hydrogen with saving energy. Benefiting from the fast charge transfer introduced by phosphide nanoarrays, the synergy in nanosheets catalysts with hetero-interface,CoxP@NiCo-LDH/Ni foam(NF) exhibits superior electrocatalytic performance(10 mA cm-2@ 1.24 V and-0.10 V for methanol selective oxidation and hydrogen evolution reaction, respectively). Furthermore,CoxP@NiCo-LDH/NF-based symmetric two-electrode electrolyzer drives a current density of 10 m A cm-2 with a low cell voltage of only 1.43 V and the Faradaic efficiency towards the generation of formate and H2 are close to 100% in the tested range of current density(from 40 to 200 m A cm-2). This work highlights the positive effect of hetero-interaction in the design of more efficient eletrocatalysts and might guide the way towards facile upgrading of alcohols and energy-saving electrolytic H2 co-generation.展开更多
Rational design of bifunctional electrocatalysts for oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)with excellent activity and stability is of great significance,since overall water splitting is a ...Rational design of bifunctional electrocatalysts for oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)with excellent activity and stability is of great significance,since overall water splitting is a promising technology for sustainable conversion of clean energy.However,most electrocatalysts do not simultaneously possess optimal HER/OER activities and their electrical conductivities are intrinsically low,which limit the development of overall water splitting.In this paper,a strategy of electric field treatment is proposed and applied to Ni/Co_(3)O_(4) film to develop a novel bifunctional electrocatalyst.After treated by electric field,the conductive channels consisting of oxygen vacancies are formed in the Co_(3)O_(4) film,which remarkably reduces the resistance of the system by almost 2×10^(4) times.Meanwhile,the surface Ni metal electrode is partially oxidized to nickel oxide,which enhances the catalytic activity.The electric-field-treated Ni/Co_(3)O_(4) material exhibits super outstanding performance of HER,OER,and overall water splitting,and the catalytic activity is significantly superior to the state-of-the-art noble metal catalysts(Pt/C,RuO_(2),and RuO_(2)‖Pt/C couple).This work provides an effective and feasible method for the development of novel and efficient bifunctional electrocatalyst,which is also promising for wide use in the field of catalysis.展开更多
The exploration of low-cost and efficient bifunctional electrocatalysts for oxygen evolution reaction and hydrogen evolution reaction through tuning the chemical composition is strongly required for sustainable resour...The exploration of low-cost and efficient bifunctional electrocatalysts for oxygen evolution reaction and hydrogen evolution reaction through tuning the chemical composition is strongly required for sustainable resources. Herein, we developed a bimetallic cobalt–manganese sulfide supported on Ni foam(CMS/Ni) via a solvothermal method. It has discovered that after combining with the pure Co_9S_8 and Mn S, the morphologies of CMS/Ni have modulated. The obtained three-dimensionally hexagram-like CMS/Ni nanosheets have a significant increase in electrochemical active surface area and charge transport ability. More than that, the synergetic effect of Co and Mn has also presented in this composite. Benefiting from these, the CMS/Ni electrode shows great performance toward hydrogen evolution reaction and oxygen evolution reaction in basic medium, comparing favorably to that ofthe pure Co_9S_8/Ni and Mn S/Ni. More importantly, this versatile CMS/Ni can catalyze the water splitting in a twoelectrode system at a potential of 1.47 V, and this electrolyzer can be efficiently driven by a 1.50 V commercial dry battery.展开更多
Bimetallic metal organic framework(MOF)as a precursor to prepare catalysts with bifunctional catalytic activity of oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)attracts more and more attention.Her...Bimetallic metal organic framework(MOF)as a precursor to prepare catalysts with bifunctional catalytic activity of oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)attracts more and more attention.Herein,hollow oxygen deficiency-enriched NiFe_(2)O_(4) is synthesized by pyrolytic FeNi bimetallic MOF.The defects of rGO during carbonization can act as nucleation sites for FeNi particles.After nucleation and N doping,the FeNi particles were served as catalysts for the deposition of dissolved carbon in the defects of the N/rGO.These deposited carbon,like a bridge,connect N/rGO and hollow oxygen deficiency-enriched NiFe_(2)O_(4) together,which giving full play to the advantages of N/rGO in fast electron transfer,thereby improving its catalytic activity.The resultant NiFe_(2)O_(4)@N/rGO-800 exhibits a low overpotential of 252 mV at 20 mA cm^(-2) for OER and 157 mV at 10 mA cm^(-2) for HER in 1 M KOH,respectively.When used as bifunctional electrodes for overall water splitting,it also shows low cell voltage of 1.60 V and 1.67 V at 10 and 20 mA cm^(-2),respectively.展开更多
The oxygen reduction/evolution reactions(ORR/OER) are a key electrode process in the development of electrochemical energy conversion and storage devices,such as metal-air batteries and reversible fuel cells.The searc...The oxygen reduction/evolution reactions(ORR/OER) are a key electrode process in the development of electrochemical energy conversion and storage devices,such as metal-air batteries and reversible fuel cells.The search for low-cost high-performance nanocarbon-based metal-free and non-precious metal bifunctional electrocatalysts for ORR/OER alternatives to the widely-used noble metal-based catalysts is a research focus.This review aims to outline the opportunities and available options for these nanocarbon-based bifunctional electrocatalysts.Through discussion of some current scientific issues,we summarize the development and breakthroughs of these electrocatalysts.Then we provide our perspectives on these issues and suggestions for some areas in the further work.We hope that this review can improve the interest in nanocarbon-based metal-free and non-precious metal bifunctional electrocatalysts for ORR/OER.展开更多
Sustainable metal-air batteries demand high-efficiency,environmentally-friendly,and non-precious metal-based electrocatalysts with bifunctionality for both the oxygen reduction reaction(ORR)and oxygen evolution reacti...Sustainable metal-air batteries demand high-efficiency,environmentally-friendly,and non-precious metal-based electrocatalysts with bifunctionality for both the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).In this research,novel functional carbon nanotubes with multi-active sites including well-dispersed single-atom iron throughout the walls and encapsulated ultrafine iron nanoparticles were synthesized as an electrocatalyst(FeNP@Fe-N-C)through one-step pyrolysis of metal-organic frameworks.High-resolution synchrotron powder X-ray diffraction and X-ray absorption spectroscopy were applied to characterize the unique structure of the electrocatalyst.In comparison to the commercial Pt/C and Ru O_(2)electrodes,the newly prepared FeNP@Fe-N-C presented a superb bifunctional performance with its narrow potential difference(Egap)of 0.73 V,which is ascribed to the metallic Fe nanoparticles that boosts the adsorption and activation of oxygen on the active sites with an enhanced O_(2)adsorption capacity of 7.88 cm^(3)g^(-1)and synergistically functionalizes the iron atoms dispersed on the nanotubes.A rechargeable zinc-air battery based on FeNP@Fe-N-C exhibited a superior open-circuit voltage(1.45 V),power density(106.5 m W cm^(-2)),and stable cycling performance.The green technique developed in this work for the fabrication of functional nanotubes raises the prospect of making more efficient electrocatalysts for sustainable energy cells.展开更多
The development of bifunctional electrocatalysts with high activity and stability for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)is crucial for efficient overall water splitting but still challe...The development of bifunctional electrocatalysts with high activity and stability for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)is crucial for efficient overall water splitting but still challenging.Herein,we propose a facile and effective polymerization–pyrolysis–selenization(PPS)strategy for in-situ synthesis of N-doped carbon nanosnakes(NCNSs)encapsulated Fe-doped CoSe nanoparticles(NPs)derived from predesigned trimetallic Zn/Fe/Co polyphthalocyanine conjugated polymer networks.Benefiting from the synergistic effect between the regulation of Fe atoms and CoSe NPs as well as the confinement effect of in situ formed porous conductive carbon nanosnakes,the FeCoSe@NCNSs catalyst exhibited the excellent electrocatalytic activity for HER with small overpotentials(142 and 99 mV in 0.5 M H_(2)SO_(4) and 1 M KOH)and OER(320 mV in 1 M KOH)at the current density of 10 mA cm^(-2).Particularly,it also can be used as an efficient bifunctional electrocatalyst with a cell voltage of 1.66 V to achieve a current density of 10 mA cm^(-2) and superior stability for overall water splitting.Density functional theory study reveals that the doping of Fe atoms on Co Se enhanced the splitting and delocalization of metal-d orbitals close Fermi level,and modifies the distribution of Se-p orbitals close Fermi level,which improved the flexibility of electron donor-acceptor system and the hydrogen adsorption free energy change on metal-metal bridge sites in FeCoSe@NCNSs.Additionally,beneficial from the accepting of Fe-Se bridge site,the overpotential of OER which following intramolecular oxygen coupling mechanism is also decreased,thus accelerating the electrocatalytic performance.This work presents a novel strategy to regulate the activity and stability of transition metal selenides and facilitating the rational design of bifunctional electrocatalysts for overall water splitting applications.展开更多
Efficient,durable and economic electrocatalysts are crucial for commercializing water electrolysis technology.Herein,we report an advanced bifunctional electrocatalyst for alkaline water splitting by growing NiFe-laye...Efficient,durable and economic electrocatalysts are crucial for commercializing water electrolysis technology.Herein,we report an advanced bifunctional electrocatalyst for alkaline water splitting by growing NiFe-layered double hydroxide(NiFe-LDH)nanosheet arrays on the conductive NiMo-based nanorods deposited on Ni foam to form a three-dimensional(3D)architecture,which exhibits exceptional performances for both hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).In overall water splitting,only the low operation voltages of 1.45/1.61 V are required to reach the current density of 10/500 mA·cm^(-2),and the continuous water splitting at an industrial-level current density of 500 mA·cm^(-2) shows a negligible degradation(1.8%)of the cell voltage over 1000 h.The outstanding performance is ascribed to the synergism of the HER-active NiMo-based nanorods and the OER-active NiFe-LDH nanosheet arrays of the hybridized 3D architecture.Specifically,the dense NiFe-LDH nanosheet arrays enhance the local pH on cathode by retarding OH-diffusion and enlarge the electrochemically active surface area on anode,while the conductive NiMo-based nanorods on Ni foam much decrease the charge-transfer resistances of both electrodes.This study provides an efficient strategy to explore advanced bifunctional electrocatalysts for overall water splitting by rationally hybridizing HER-and OER-active components.展开更多
As the cleanest energy source,hydrogen energy is regarded as the most promising fuel.Water electrolysis,as the primary means of hydrogen production,has constantly been the focus of attention in the energy conversion f...As the cleanest energy source,hydrogen energy is regarded as the most promising fuel.Water electrolysis,as the primary means of hydrogen production,has constantly been the focus of attention in the energy conversion field.Developing eco-friendly,cheap,safe and efficient catalysts for electrochemical water splitting(EWS)is the key challenge.Herein,the intermetallic silicide alloy is first synthesized via a facile magnesiothermic reduction and employed as bifunctional electrocatalysts for EWS.Ferric-nickel silicide(denoted as FeNiSi)alloy is designed and shows a good electrocatalytic performance for EWS.The lattice distortions of FeNiSi enhance the electrocatalytic activity.Besides,the porous structure affords more active sites and improves the reaction kinetics.As a consequence,FeNiSi delivers an excellent performance with overpotential of 308 mV for oxygen evolution reaction(OER)and 386 mV for hydrogen evolution reaction(HER)at 10 mA·cm−2 in 1 M KOH.The stability structure of intermetallic silicide achieves an outstanding durability with an unchanged potential of 1.66 V for overall water splitting at 10 mA·cm−2 for 15 h.This work not only provides a facile method for the synthesis of intermetallic silicide with considerable porous structures,but also develops the potential of intermetallic silicide alloy as bifunctional electrocatalysts for EWS,which opens up a new avenue for the design and application of intermetallic silicide alloy.展开更多
Fe-nitrogen-carbon(Fe-N-C)-and Co-nitrogen-carbon(Co-N-C)-based electrocatalysts have been widely concerned because of their high OER/ORR activity,low metal cost,and simple preparation.The exploration of Fe-N-C and Co...Fe-nitrogen-carbon(Fe-N-C)-and Co-nitrogen-carbon(Co-N-C)-based electrocatalysts have been widely concerned because of their high OER/ORR activity,low metal cost,and simple preparation.The exploration of Fe-N-C and Co-N-C single atombased catalysts with high activity and stability to overcome the slow kinetics of oxygen reduction and oxygen evolution reactions is also the key to the development of efficient electrolytic water,fuel cells,and rechargeable metal-air batteries.Fe-N-C and Co-N-C single atom-based electrocatalysts have the advantages of a high utilization rate of metal atoms and high electrocatalytic activity,and are ideal catalysts for promoting electrochemical energy conversion and storage.The general principles of designing Fe-N-C and Co-N-C single atom-based electrocatalysts are reviewed in this paper.Then,the strategies to improve the bifunctional catalytic activity and stability are proposed.Finally,the challenges and prospects of Fe-N-C and Co-N-C single atom-based catalysts are well summarized.This review will provide a reference for the directed optimization of Fe-N-C and Co-N-C single atom-based catalysts.展开更多
Zinc-air batteries(ZABs)are regarded as promising next-generation energy storage devices but limited by their sluggish oxygen reduction/evolution reactions(ORR/OER).Herein,the bifunctional catalyst consisting of MXene...Zinc-air batteries(ZABs)are regarded as promising next-generation energy storage devices but limited by their sluggish oxygen reduction/evolution reactions(ORR/OER).Herein,the bifunctional catalyst consisting of MXene and metal compounds has been constructed via a controllable strategy.For demonstration,a 3D MXene framework with anchored heterostructure CoNi/CoNiP and nitrogen-doped carbon(NC)called H-CNP@M is constructed by metal-ion inducement and phosphorization.The bimetal-semiconductor heterostructure greatly enhances the catalytic performance.The H-CNP@M exhibits superior activities to-Ward ORR(E_(i/2)=0.833V)and OER(η_(10)=294 mV).Both aqueous and all-solid-state ZAB assembled with H-CNP@M demonstrate superior performance(peak power density of 166.5 mW/cm^(2)in aqueous case).This work provides a facile and general strategy to prepare MXene-supported bimetallic heterostructure for high-performance electrochemical energy devices.展开更多
Developing bifunctional electrocatalysts for overall water splitting reaction is still highly desired but with large challenges. Herein, an amorphous Fe Co Ni-S electrocatalyst was developed using thioacetamide for th...Developing bifunctional electrocatalysts for overall water splitting reaction is still highly desired but with large challenges. Herein, an amorphous Fe Co Ni-S electrocatalyst was developed using thioacetamide for the sulfuration of Fe Co Ni hydroxide during the hydrothermal process. The obtained catalyst exhibited an amorphous structure with hybrid bonds of metal-S bond and metal-O bonds in the catalyst system. The optimized catalyst showed a largely improved bifunctional catalytic ability to drive water splitting reaction in the alkaline electrolyte compared to the Fe Co Ni hydroxide. It required an overpotential of 280 m V and 80 m V(No-IR correction) to offer 10 m A/cm^(2)for water oxidation and reduction respectively;a low cell voltage of 1.55 V was required to reach 10 m A/cm^(2)for the water electrolysis with good stability for12 h. Moreover, this catalyst system showed high catalytic stability, catalytic kinetics, and Faraday efficiency for water splitting reactions. Considering the very low intrinsic activity of Fe Co Ni hydroxide, the efficient bifunctional catalytic ability should result from the newly formed hybrid active sites of metallic metal-S species and the high valence state of metal oxide species. This work is effective in the bifunctional catalytic ability boosting for the transition metal materials by facile sulfuration in the hydrothermal approach.展开更多
metal oxide electronic interactions in composite electrocatalysts have a considerable impact on their catalytic capability.In this study,we successfully synthesized an electrocatalytic material composed of MoO_(3)/C s...metal oxide electronic interactions in composite electrocatalysts have a considerable impact on their catalytic capability.In this study,we successfully synthesized an electrocatalytic material composed of MoO_(3)/C speciessupported Pd nanoparticles(Pd-MoO_(3)/C)using a convenient hydrothermal method,which exhibited excellent catalytic activities for both ethanol oxidation and oxygen reduction in KOH media.The specific activity of PdMoO_(3)/C toward ethanol oxidation with MoO_(3)loading(40wt%)was~2.6 times greater than that for the commercial Pd/C(10 wt%)with the same Pd content.In particular,the activity could effectively hold up to~60%of its maximum activity after 500-cycle tests,demonstrating improved cyclical stability.Notably,the fast electron transfer kinetics toward oxygen reduction for Pd-MoO_(3)/C(40%)were also comparable to those of commercial Pt/C(20 wt%)catalysts.These superior electrochemical features are primarily derived from the stronger electronic coupling between Pd and MoO_(3)through charge transfer,which can supply more active centers and improve the anti-poisoning ability.Meanwhile,the MoO_(3)species in the Pd-MoO_(3)/C composite may provide additional benefits in terms of electrical conductivity and dispersion.展开更多
Given the current shortage of resources and environmental pollution,rationally designing and developing low-cost and highefficiency bifunctional electrocatalysts is an urgent and challenging task.It is widely recogniz...Given the current shortage of resources and environmental pollution,rationally designing and developing low-cost and highefficiency bifunctional electrocatalysts is an urgent and challenging task.It is widely recognized that element doping can effectively improve the electrocatalytic activity by adjusting the microstructure,morphology,and electronic structure.Therefore,this work rationally designs and prepares three-dimensional flower-like structured W-doped FeNi_(2)S_(4)/Ni_(3)S_(2)/NF heterojunctions as efficient bifunctional electrocatalysts for overall water splitting.In 1 M KOH,the prepared W-FeNi_(2)S_(4)/Ni_(3)S_(2)/NF electrocatalyst can effectively drive both hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)processes,and only needs overpotentials of 93 and 210 mV to reach current densities of 10 and 50 mA·cm^(−2).In the double electrode cell composed by WFeNi_(2)S_(4)/Ni_(3)S_(2)/NF electrocatalyst,a low cell voltage of 1.52 V was required to reach a current density of 10 mA·cm^(−2),and 91.6%of this value was preserved after 24 h electrolysis operation.The performance of FeNi_(2)S_(4)/Ni_(3)S_(2)/NF electrocatalyst is superior to most of the current bifunctional electrocatalytic materials.Density functional theory(DFT)theoretical calculations also revealed a more intense electron transfer process that can be facilitated by constructing FeNi_(2)S_(4)and Ni_(3)S_(2)/NF interface,which may be the main reason for the archived excellent electrochemical performance.展开更多
Efficient and robust noble-metal-free bifunctional electrocatalysts for overall water splitting(OWS)is of great importance to realize the large-scale hydrogen production.Herein,we report the growth of undoped and Cr-d...Efficient and robust noble-metal-free bifunctional electrocatalysts for overall water splitting(OWS)is of great importance to realize the large-scale hydrogen production.Herein,we report the growth of undoped and Cr-doped NiCo2O4(Cr-NiCo2O4)nanoneedles(NNs)on nickel foam(NF)as bifunctional electrocatalysts for both hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).We demonstrate that Cr-doping significantly improves activity for HER and OER by increasing the conductivity of NNs and allowing more active sites on NNs electrochemically accessible.When amorphous FeOOH is electrodeposited on the surface of Cr-NiCo2O4 NNs,the resulting FeOOH/Cr-NiCo2O4/NF exhibits itself as an excellent bifunctional catalyst for OWS.In the two-electrode cell where FeOOH/Cr-NiCo2O4/NF is used both as cathode and anode for OWS,a cell voltage of only 1.65 V is required to achieve an electrolysis current density of 100 mA·cm^−2.In addition,the catalyst shows a very high stability for OWS,the two-electrode cell can operate at a consist current density of 20 mA·cm^−2 for 10 h OWS with the cell voltage being stable at ca.1.60 V.These results demonstrate that FeOOH/Cr-NiCo2O4/NF possesses an OWS performance superior to most of transition-metal based bifunctional electrocatalysts working in alkaline medium.The excellent bifunctional activity and stability of FeOOH/Cr-NiCo2O4/NF are attributed to the following reasons:(i)The NN structure provides a large specific surface area;(ii)the high conductivity of Cr-NiCo2O4 enables more active centers on the far-end part of NNs to be electrochemically reached;(iii)the deposition of FeOOH supplies additional active sites for OWS.展开更多
To develop more ideal bifunctional heteroatom-doped carbon electrocatalysts toward the oxygen reduction reaction(ORR) and oxygen evolution reaction(OER) for regenerative fuel cells and rechargeable metal–air batterie...To develop more ideal bifunctional heteroatom-doped carbon electrocatalysts toward the oxygen reduction reaction(ORR) and oxygen evolution reaction(OER) for regenerative fuel cells and rechargeable metal–air batteries, herein, tobacco-derived N-containing ordered mesoporous carbon(N-OMC) electrocatalysts with different N species distributions are designed. Results indicate that the as-prepared N-OMC with more pyrrolic and pyridinic Ns exhibits much higher activities for the ORR and OER than N-OMC with more graphitic N in both acidic and alkaline media, suggesting that the increase of pyrrolic and pyridinic Ns favors the improvement of ORR and OER activities of the N-containing carbon catalysts, and showing a great potential for the designing of more effective, lower-cost ORR and OER bifunctional electrocatalysts for future regenerative fuel cells and rechargeable metal–air batteries.展开更多
The strategy of adopting cheap precursors or abundant resources,which can be obtained directly from nature,is a simple and excellent method of introducing accessible research into environmentally friendly development....The strategy of adopting cheap precursors or abundant resources,which can be obtained directly from nature,is a simple and excellent method of introducing accessible research into environmentally friendly development.Moreover,this is also an urgent requirement for the sustainable development of green technology.Herein,we introduce a simplistic and expandable method to prepare metal-free biomassderived nitrogen self-doped porous activation carbon(N-PAC) with large specific surface area(S_(BET)=1300.58 m^(2)/g).Moreover,the manufactural electrocatalysts exhibit prominent oxygen reduction reaction(ORR) performance in all PH values.As compared with the commercial Pt/C catalyst,the N-PAC/800 with a positive onset potential at 10 mA/cm^(2)(0.93 V),half-wave potential(0.87 V),and limiting current(6.34 mA/cm^(2)) bring to light excellent catalytic stability,selectivity,and much-enhanced methanol tolerance.Furthermore,the prepared electrocatalysts possess considerable hydrogen evolution reaction(HER) performance with a less onset potential of 0.218 V(acidic medium) and0.271 V(alkaline medium) respectively,which can show similar catalytic activity across the whole pH range.Such bifunctional electrocatalyst,with excellent electrocatalytic properties,resource-rich,low cost,and environmental-friendly,hold a promising application in energy conversion and reserve.展开更多
基金Iran National Science Foundation(INSF)under project No.4025105the Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering(Grant No.2022-K31)+1 种基金the Zhejiang Province Key Research and Development Project(2023 C01191)Alexander M.Kirillov acknowledges the Foundation for Science and Technology(LISBOA-01-0145-FEDER-029697,PTDC/QUIQIN/3898/2020,LA/P/0056/2020,UIDB/00100/2020).
文摘Water-splitting reactions such as the hydrogen evolution reaction(HER)and the oxygen evolution reaction(OER)typically require expensive noble metal-based electrocatalysts.This has motivated researchers to develop novel,cost-effective electrocatalytic systems.In this study,a new multicomponent nanocomposite was assembled by combining functionalized multiwalled carbon nanotubes,a Cu-based metal–organic framework(MOF)(HKUST-1 or HK),and a sulfidized NiMn-layered double hydroxide(NiMn-S).The resulting nanocomposite,abbreviated as MW/HK/NiMn-S,features a unique architecture,high porosity,numerous electroactive Cu/Ni/Mn sites,fast charge transfer,excellent structural stability,and conductivity.At a current density of 10 mA cm-2,this dual-function electrocatalyst shows remarkable performance,with ultralow overpotential values of 163 mV(OER)or 73 mV(HER),as well as low Tafel slopes(57 and 75 mV dec-1,respectively).Additionally,its high turnover frequency values(4.43 s-1 for OER;3.96 s-1 for HER)are significantly superior to those of standard noble metal-based Pt/C and IrO2 systems.The synergistic effect of the nanocomposite's different components is responsible for its enhanced electrocatalytic performance.A density functional theory study revealed that the multi-interface and multicomponent heterostructure contribute to increased electrical conductivity and decreased energy barrier,resulting in superior electrocatalytic HER/OER activity.This study presents a novel vision for designing advanced electrocatalysts with superior performance in water splitting.Various composites have been utilized in water-splitting applications.This study investigates the use of the MW/HK/NiMn-S electrocatalyst for water splitting for the first time to indicate the synergistic effect between carbon-based materials along with layered double hydroxide compounds and porous compounds of MOF.The unique features of each component in this composite can be an interesting topic in the field of water splitting.
基金The authors acknowledge the National Natural Science Foundation of China(NSFC 91834301,21808046 and 21908037)Anhui Provincial Science and Technology Department Foundation(201903a05020021 and 202003a05020046)for funding support.
文摘Improving catalytic activity and durabilty through the structural and compositional development of bifunctional electrocatalysts with low cost,high activity and stability is a challenging issue in electrochemical water splitting.Herein,we report the fabrication of heterostructured P-CoMoO_(4)@NiCoP on a Ni foam substrate through interface engineering,by adjusting its composition and architecture.Benefitting from the tailored electronic structure and exposed active sites,the heterostructured P-CoMoO_(4)@NiCoP/NF arrays can be coordinated to boost the overall water splitting.In addition,the superhydrophilic and superaerophobic properties of P-CoMoO_(4)@NiCoP/NF make it conducive to water dissociation and bubble separation in the electrocatalytic process.The heterostructured PCoMoO_(4)@NiCoP/NF exhibits excellent bifunctional electrocatalysis activity with a low overpotential of 66 mV at 10 mA cm^(-2) for HER and 252 mV at 100 mA cm^(-2) for OER.Only 1.62 V potential is required to deliver 20 mA cm^(-2) in a two-electrode electrolysis system,providing a decent overall water splitting performance.The rational construction of the heterostructure makes it possible to regulate the electronic structures and active sites of the electrocatalysts to promote their catalytic activity.
基金Youth Innovation Promotion Association of the Chinese Academy of Sciences,Grant/Award Number:2021174National Natural Science Foundation of China,Grant/Award Number:51902326Natural Science Foundation of Shanxi Province,Grant/Award Numbers:201901D211588,20210302124421。
文摘Transition-metal phosphides(TMPs)with high catalytic activity are widely used in the design of electrodes for water splitting.However,a major challenge is how to achieve the trade-off between activity and stability of TMPs.Herein,a novel method for synthesizing CoP nanoparticles encapsu-lated in a rich-defect carbon shell(CoP/DCS)is developed through the self-assembly of modified polycyclic aromatic molecules.The graft and removal of high-activity C-N bonds of aromatic molecules render the controllable design of crystallite defects of carbon shell.The density functional theory calculation indicates that the carbon defects with unpaired electrons could effectively tailor the band structure of CoP.Benefiting from the improved activity and corrosion resistance,the CoP/DCS delivers outstanding difunctional hydrogen evolution reaction(88 mV)and oxygen evolution reaction(251 mV)performances at 10 mA cm^(−2)current density.Furthermore,the coupled water electrolyzer with CoP/DCS as both the cathode and anode presents ultralow cell voltages of 1.49 V to achieve 10 mA cm^(−2)with long-time stability.This strategy to improve TMPs electrocatalyst with rich-DCS and heterogeneous structure will inspire the design of other transition metal compound electrocatalysts for water splitting.
基金financially supported by the National Natural Science Foundation of China(Nos.21975163 and 21905181)。
文摘The inefficiency of water splitting is mainly due to the sluggish anodic water oxidation reaction. Replacing water oxidation with thermodynamically more favorable selective methanol oxidation reaction and developing robust bifunctional electrocatalysts are of great significance. Herein, a hierarchical heteronanostructure with Ni–Co layered double hydroxide(LDH) ultrathin nanosheets coated on cobalt phosphide nanosheets arrays(CoxP@NiCo-LDH) are fabricated and used for co-electrolysis of methanol/water to co-produce value-added formate and hydrogen with saving energy. Benefiting from the fast charge transfer introduced by phosphide nanoarrays, the synergy in nanosheets catalysts with hetero-interface,CoxP@NiCo-LDH/Ni foam(NF) exhibits superior electrocatalytic performance(10 mA cm-2@ 1.24 V and-0.10 V for methanol selective oxidation and hydrogen evolution reaction, respectively). Furthermore,CoxP@NiCo-LDH/NF-based symmetric two-electrode electrolyzer drives a current density of 10 m A cm-2 with a low cell voltage of only 1.43 V and the Faradaic efficiency towards the generation of formate and H2 are close to 100% in the tested range of current density(from 40 to 200 m A cm-2). This work highlights the positive effect of hetero-interaction in the design of more efficient eletrocatalysts and might guide the way towards facile upgrading of alcohols and energy-saving electrolytic H2 co-generation.
基金supported by the program B for Outstanding PhD candidate of Nanjing University.
文摘Rational design of bifunctional electrocatalysts for oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)with excellent activity and stability is of great significance,since overall water splitting is a promising technology for sustainable conversion of clean energy.However,most electrocatalysts do not simultaneously possess optimal HER/OER activities and their electrical conductivities are intrinsically low,which limit the development of overall water splitting.In this paper,a strategy of electric field treatment is proposed and applied to Ni/Co_(3)O_(4) film to develop a novel bifunctional electrocatalyst.After treated by electric field,the conductive channels consisting of oxygen vacancies are formed in the Co_(3)O_(4) film,which remarkably reduces the resistance of the system by almost 2×10^(4) times.Meanwhile,the surface Ni metal electrode is partially oxidized to nickel oxide,which enhances the catalytic activity.The electric-field-treated Ni/Co_(3)O_(4) material exhibits super outstanding performance of HER,OER,and overall water splitting,and the catalytic activity is significantly superior to the state-of-the-art noble metal catalysts(Pt/C,RuO_(2),and RuO_(2)‖Pt/C couple).This work provides an effective and feasible method for the development of novel and efficient bifunctional electrocatalyst,which is also promising for wide use in the field of catalysis.
基金supported by National Natural Science Foundation of China(21576113 and 21376105)Foshan Innovative and Entrepreneurial Research Team Program(No.2014IT100062)
文摘The exploration of low-cost and efficient bifunctional electrocatalysts for oxygen evolution reaction and hydrogen evolution reaction through tuning the chemical composition is strongly required for sustainable resources. Herein, we developed a bimetallic cobalt–manganese sulfide supported on Ni foam(CMS/Ni) via a solvothermal method. It has discovered that after combining with the pure Co_9S_8 and Mn S, the morphologies of CMS/Ni have modulated. The obtained three-dimensionally hexagram-like CMS/Ni nanosheets have a significant increase in electrochemical active surface area and charge transport ability. More than that, the synergetic effect of Co and Mn has also presented in this composite. Benefiting from these, the CMS/Ni electrode shows great performance toward hydrogen evolution reaction and oxygen evolution reaction in basic medium, comparing favorably to that ofthe pure Co_9S_8/Ni and Mn S/Ni. More importantly, this versatile CMS/Ni can catalyze the water splitting in a twoelectrode system at a potential of 1.47 V, and this electrolyzer can be efficiently driven by a 1.50 V commercial dry battery.
基金financially supported by the National Natural Science Foundation of China(Nos.21878231,21676202 and 51603145)Natural Science Foundation of Tianjin(Nos.19JCZDJC37300 and 17JCZDJC38100)supported by the Science and Technology Plans of Tianjin(Nos.17PTSYJC00040 and 18PTSYJC00180)。
文摘Bimetallic metal organic framework(MOF)as a precursor to prepare catalysts with bifunctional catalytic activity of oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)attracts more and more attention.Herein,hollow oxygen deficiency-enriched NiFe_(2)O_(4) is synthesized by pyrolytic FeNi bimetallic MOF.The defects of rGO during carbonization can act as nucleation sites for FeNi particles.After nucleation and N doping,the FeNi particles were served as catalysts for the deposition of dissolved carbon in the defects of the N/rGO.These deposited carbon,like a bridge,connect N/rGO and hollow oxygen deficiency-enriched NiFe_(2)O_(4) together,which giving full play to the advantages of N/rGO in fast electron transfer,thereby improving its catalytic activity.The resultant NiFe_(2)O_(4)@N/rGO-800 exhibits a low overpotential of 252 mV at 20 mA cm^(-2) for OER and 157 mV at 10 mA cm^(-2) for HER in 1 M KOH,respectively.When used as bifunctional electrodes for overall water splitting,it also shows low cell voltage of 1.60 V and 1.67 V at 10 and 20 mA cm^(-2),respectively.
基金the financial support provided by the National Natural Science Foundation of China(Grant Nos.51932005 and 21773269)the Joint Research Fund LiaoningShenyang National Laboratory for Materials Science(Grant No.20180510047)Liao Ning Revitalization Talents Program(XLYC1807175)。
文摘The oxygen reduction/evolution reactions(ORR/OER) are a key electrode process in the development of electrochemical energy conversion and storage devices,such as metal-air batteries and reversible fuel cells.The search for low-cost high-performance nanocarbon-based metal-free and non-precious metal bifunctional electrocatalysts for ORR/OER alternatives to the widely-used noble metal-based catalysts is a research focus.This review aims to outline the opportunities and available options for these nanocarbon-based bifunctional electrocatalysts.Through discussion of some current scientific issues,we summarize the development and breakthroughs of these electrocatalysts.Then we provide our perspectives on these issues and suggestions for some areas in the further work.We hope that this review can improve the interest in nanocarbon-based metal-free and non-precious metal bifunctional electrocatalysts for ORR/OER.
基金financially supported by grants 17210219 and T21-711/16R from the Research Grants Council of the Hong Kong governmentproject 51978369 from the National Natural Science Foundation of China。
文摘Sustainable metal-air batteries demand high-efficiency,environmentally-friendly,and non-precious metal-based electrocatalysts with bifunctionality for both the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).In this research,novel functional carbon nanotubes with multi-active sites including well-dispersed single-atom iron throughout the walls and encapsulated ultrafine iron nanoparticles were synthesized as an electrocatalyst(FeNP@Fe-N-C)through one-step pyrolysis of metal-organic frameworks.High-resolution synchrotron powder X-ray diffraction and X-ray absorption spectroscopy were applied to characterize the unique structure of the electrocatalyst.In comparison to the commercial Pt/C and Ru O_(2)electrodes,the newly prepared FeNP@Fe-N-C presented a superb bifunctional performance with its narrow potential difference(Egap)of 0.73 V,which is ascribed to the metallic Fe nanoparticles that boosts the adsorption and activation of oxygen on the active sites with an enhanced O_(2)adsorption capacity of 7.88 cm^(3)g^(-1)and synergistically functionalizes the iron atoms dispersed on the nanotubes.A rechargeable zinc-air battery based on FeNP@Fe-N-C exhibited a superior open-circuit voltage(1.45 V),power density(106.5 m W cm^(-2)),and stable cycling performance.The green technique developed in this work for the fabrication of functional nanotubes raises the prospect of making more efficient electrocatalysts for sustainable energy cells.
基金supported by the Taishan Scholars Program of Shandong Province (No. tsqn201909065)the National Natural Science Foundation of China (No. 22108306)+3 种基金the Shandong Provincial Natural Science Foundation (ZR2020QB174, ZR2021YQ15)the Postgraduate Innovation Fund of China University of Petroleum(East China)(No. YCX2020037)the State Key Laboratory of Organic-Inorganic Composites (oic-202101006)the Key Laboratory of Functional Inorganic Material Chemistry (Heilongjiang University),Ministry of Education。
文摘The development of bifunctional electrocatalysts with high activity and stability for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)is crucial for efficient overall water splitting but still challenging.Herein,we propose a facile and effective polymerization–pyrolysis–selenization(PPS)strategy for in-situ synthesis of N-doped carbon nanosnakes(NCNSs)encapsulated Fe-doped CoSe nanoparticles(NPs)derived from predesigned trimetallic Zn/Fe/Co polyphthalocyanine conjugated polymer networks.Benefiting from the synergistic effect between the regulation of Fe atoms and CoSe NPs as well as the confinement effect of in situ formed porous conductive carbon nanosnakes,the FeCoSe@NCNSs catalyst exhibited the excellent electrocatalytic activity for HER with small overpotentials(142 and 99 mV in 0.5 M H_(2)SO_(4) and 1 M KOH)and OER(320 mV in 1 M KOH)at the current density of 10 mA cm^(-2).Particularly,it also can be used as an efficient bifunctional electrocatalyst with a cell voltage of 1.66 V to achieve a current density of 10 mA cm^(-2) and superior stability for overall water splitting.Density functional theory study reveals that the doping of Fe atoms on Co Se enhanced the splitting and delocalization of metal-d orbitals close Fermi level,and modifies the distribution of Se-p orbitals close Fermi level,which improved the flexibility of electron donor-acceptor system and the hydrogen adsorption free energy change on metal-metal bridge sites in FeCoSe@NCNSs.Additionally,beneficial from the accepting of Fe-Se bridge site,the overpotential of OER which following intramolecular oxygen coupling mechanism is also decreased,thus accelerating the electrocatalytic performance.This work presents a novel strategy to regulate the activity and stability of transition metal selenides and facilitating the rational design of bifunctional electrocatalysts for overall water splitting applications.
基金supported by the National Key Research and Development Program of China(No.2021YFA1500900)the National Natural Science Foundation of China(Nos.52071174,21832003,21972061)+1 种基金the Natural Science Foundation of Jiangsu Province,Major Project(No.BK20212005)the Foundation of Science and Technology of Suzhou(No.SYC2022102).
文摘Efficient,durable and economic electrocatalysts are crucial for commercializing water electrolysis technology.Herein,we report an advanced bifunctional electrocatalyst for alkaline water splitting by growing NiFe-layered double hydroxide(NiFe-LDH)nanosheet arrays on the conductive NiMo-based nanorods deposited on Ni foam to form a three-dimensional(3D)architecture,which exhibits exceptional performances for both hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).In overall water splitting,only the low operation voltages of 1.45/1.61 V are required to reach the current density of 10/500 mA·cm^(-2),and the continuous water splitting at an industrial-level current density of 500 mA·cm^(-2) shows a negligible degradation(1.8%)of the cell voltage over 1000 h.The outstanding performance is ascribed to the synergism of the HER-active NiMo-based nanorods and the OER-active NiFe-LDH nanosheet arrays of the hybridized 3D architecture.Specifically,the dense NiFe-LDH nanosheet arrays enhance the local pH on cathode by retarding OH-diffusion and enlarge the electrochemically active surface area on anode,while the conductive NiMo-based nanorods on Ni foam much decrease the charge-transfer resistances of both electrodes.This study provides an efficient strategy to explore advanced bifunctional electrocatalysts for overall water splitting by rationally hybridizing HER-and OER-active components.
基金the Natural Science Foundation of Liaoning Province(No.2023-MS-115)and Large Instrument and Equipment Open Foundation of Dalian University of Technology.
文摘As the cleanest energy source,hydrogen energy is regarded as the most promising fuel.Water electrolysis,as the primary means of hydrogen production,has constantly been the focus of attention in the energy conversion field.Developing eco-friendly,cheap,safe and efficient catalysts for electrochemical water splitting(EWS)is the key challenge.Herein,the intermetallic silicide alloy is first synthesized via a facile magnesiothermic reduction and employed as bifunctional electrocatalysts for EWS.Ferric-nickel silicide(denoted as FeNiSi)alloy is designed and shows a good electrocatalytic performance for EWS.The lattice distortions of FeNiSi enhance the electrocatalytic activity.Besides,the porous structure affords more active sites and improves the reaction kinetics.As a consequence,FeNiSi delivers an excellent performance with overpotential of 308 mV for oxygen evolution reaction(OER)and 386 mV for hydrogen evolution reaction(HER)at 10 mA·cm−2 in 1 M KOH.The stability structure of intermetallic silicide achieves an outstanding durability with an unchanged potential of 1.66 V for overall water splitting at 10 mA·cm−2 for 15 h.This work not only provides a facile method for the synthesis of intermetallic silicide with considerable porous structures,but also develops the potential of intermetallic silicide alloy as bifunctional electrocatalysts for EWS,which opens up a new avenue for the design and application of intermetallic silicide alloy.
基金supported by NSFC(52373215)Sichuan Science and Technology Program(2023NSFSC0086)Fundamental Research Funds for the Central Universities(YJ2021156)。
文摘Fe-nitrogen-carbon(Fe-N-C)-and Co-nitrogen-carbon(Co-N-C)-based electrocatalysts have been widely concerned because of their high OER/ORR activity,low metal cost,and simple preparation.The exploration of Fe-N-C and Co-N-C single atombased catalysts with high activity and stability to overcome the slow kinetics of oxygen reduction and oxygen evolution reactions is also the key to the development of efficient electrolytic water,fuel cells,and rechargeable metal-air batteries.Fe-N-C and Co-N-C single atom-based electrocatalysts have the advantages of a high utilization rate of metal atoms and high electrocatalytic activity,and are ideal catalysts for promoting electrochemical energy conversion and storage.The general principles of designing Fe-N-C and Co-N-C single atom-based electrocatalysts are reviewed in this paper.Then,the strategies to improve the bifunctional catalytic activity and stability are proposed.Finally,the challenges and prospects of Fe-N-C and Co-N-C single atom-based catalysts are well summarized.This review will provide a reference for the directed optimization of Fe-N-C and Co-N-C single atom-based catalysts.
基金supported by Natural Science Foundation of Jiangsu Province(No.BK20200406)National Natural Science Foundation of China(Nos.51731004,22075263,52002366)+2 种基金National Key R&D Program of China(No.2021YFA1501502)the Fundamental Research Funds for the Central Universities(No.WK2060000039)the Collaborative Research Fund(No.C5031-20G)from Research Grant Council,University Grants Committee,Hong Kong SAR,and Project of Strategic Importance Program of The Hong Kong Polytechnic University(No.P0035168).
文摘Zinc-air batteries(ZABs)are regarded as promising next-generation energy storage devices but limited by their sluggish oxygen reduction/evolution reactions(ORR/OER).Herein,the bifunctional catalyst consisting of MXene and metal compounds has been constructed via a controllable strategy.For demonstration,a 3D MXene framework with anchored heterostructure CoNi/CoNiP and nitrogen-doped carbon(NC)called H-CNP@M is constructed by metal-ion inducement and phosphorization.The bimetal-semiconductor heterostructure greatly enhances the catalytic performance.The H-CNP@M exhibits superior activities to-Ward ORR(E_(i/2)=0.833V)and OER(η_(10)=294 mV).Both aqueous and all-solid-state ZAB assembled with H-CNP@M demonstrate superior performance(peak power density of 166.5 mW/cm^(2)in aqueous case).This work provides a facile and general strategy to prepare MXene-supported bimetallic heterostructure for high-performance electrochemical energy devices.
基金supported by the National Natural Science Foundation of China (No. 21972124)the Priority Academic Program Development of Jiangsu Higher Education Institutionthe support of the Six Talent Peaks Project of Jiangsu Province (No. XCL-070–2018)。
文摘Developing bifunctional electrocatalysts for overall water splitting reaction is still highly desired but with large challenges. Herein, an amorphous Fe Co Ni-S electrocatalyst was developed using thioacetamide for the sulfuration of Fe Co Ni hydroxide during the hydrothermal process. The obtained catalyst exhibited an amorphous structure with hybrid bonds of metal-S bond and metal-O bonds in the catalyst system. The optimized catalyst showed a largely improved bifunctional catalytic ability to drive water splitting reaction in the alkaline electrolyte compared to the Fe Co Ni hydroxide. It required an overpotential of 280 m V and 80 m V(No-IR correction) to offer 10 m A/cm^(2)for water oxidation and reduction respectively;a low cell voltage of 1.55 V was required to reach 10 m A/cm^(2)for the water electrolysis with good stability for12 h. Moreover, this catalyst system showed high catalytic stability, catalytic kinetics, and Faraday efficiency for water splitting reactions. Considering the very low intrinsic activity of Fe Co Ni hydroxide, the efficient bifunctional catalytic ability should result from the newly formed hybrid active sites of metallic metal-S species and the high valence state of metal oxide species. This work is effective in the bifunctional catalytic ability boosting for the transition metal materials by facile sulfuration in the hydrothermal approach.
基金financially supported by the Natural Science Foundation of Shanxi Province(No.201901D111277)the National Natural Science Foundation of China(No.21571119)+1 种基金the Graduate Science and Technology Innovation Project Foundation of Shanxi Normal University(No.2021DCXM71)the Program for New Century Excellent Talents in University(No.NCET-12-1035)。
文摘metal oxide electronic interactions in composite electrocatalysts have a considerable impact on their catalytic capability.In this study,we successfully synthesized an electrocatalytic material composed of MoO_(3)/C speciessupported Pd nanoparticles(Pd-MoO_(3)/C)using a convenient hydrothermal method,which exhibited excellent catalytic activities for both ethanol oxidation and oxygen reduction in KOH media.The specific activity of PdMoO_(3)/C toward ethanol oxidation with MoO_(3)loading(40wt%)was~2.6 times greater than that for the commercial Pd/C(10 wt%)with the same Pd content.In particular,the activity could effectively hold up to~60%of its maximum activity after 500-cycle tests,demonstrating improved cyclical stability.Notably,the fast electron transfer kinetics toward oxygen reduction for Pd-MoO_(3)/C(40%)were also comparable to those of commercial Pt/C(20 wt%)catalysts.These superior electrochemical features are primarily derived from the stronger electronic coupling between Pd and MoO_(3)through charge transfer,which can supply more active centers and improve the anti-poisoning ability.Meanwhile,the MoO_(3)species in the Pd-MoO_(3)/C composite may provide additional benefits in terms of electrical conductivity and dispersion.
基金the National Key R&D Program of China(Nos.2021YFA1501300 and 2019YFC1907602)the National Natural Science Foundation of China(Nos.51572295,21273285,and 21003157).
文摘Given the current shortage of resources and environmental pollution,rationally designing and developing low-cost and highefficiency bifunctional electrocatalysts is an urgent and challenging task.It is widely recognized that element doping can effectively improve the electrocatalytic activity by adjusting the microstructure,morphology,and electronic structure.Therefore,this work rationally designs and prepares three-dimensional flower-like structured W-doped FeNi_(2)S_(4)/Ni_(3)S_(2)/NF heterojunctions as efficient bifunctional electrocatalysts for overall water splitting.In 1 M KOH,the prepared W-FeNi_(2)S_(4)/Ni_(3)S_(2)/NF electrocatalyst can effectively drive both hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)processes,and only needs overpotentials of 93 and 210 mV to reach current densities of 10 and 50 mA·cm^(−2).In the double electrode cell composed by WFeNi_(2)S_(4)/Ni_(3)S_(2)/NF electrocatalyst,a low cell voltage of 1.52 V was required to reach a current density of 10 mA·cm^(−2),and 91.6%of this value was preserved after 24 h electrolysis operation.The performance of FeNi_(2)S_(4)/Ni_(3)S_(2)/NF electrocatalyst is superior to most of the current bifunctional electrocatalytic materials.Density functional theory(DFT)theoretical calculations also revealed a more intense electron transfer process that can be facilitated by constructing FeNi_(2)S_(4)and Ni_(3)S_(2)/NF interface,which may be the main reason for the archived excellent electrochemical performance.
基金We gratefully acknowledge the financial support of this work by the National Natural Science Foundation of China(Nos.51872015 and 51672017).
文摘Efficient and robust noble-metal-free bifunctional electrocatalysts for overall water splitting(OWS)is of great importance to realize the large-scale hydrogen production.Herein,we report the growth of undoped and Cr-doped NiCo2O4(Cr-NiCo2O4)nanoneedles(NNs)on nickel foam(NF)as bifunctional electrocatalysts for both hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).We demonstrate that Cr-doping significantly improves activity for HER and OER by increasing the conductivity of NNs and allowing more active sites on NNs electrochemically accessible.When amorphous FeOOH is electrodeposited on the surface of Cr-NiCo2O4 NNs,the resulting FeOOH/Cr-NiCo2O4/NF exhibits itself as an excellent bifunctional catalyst for OWS.In the two-electrode cell where FeOOH/Cr-NiCo2O4/NF is used both as cathode and anode for OWS,a cell voltage of only 1.65 V is required to achieve an electrolysis current density of 100 mA·cm^−2.In addition,the catalyst shows a very high stability for OWS,the two-electrode cell can operate at a consist current density of 20 mA·cm^−2 for 10 h OWS with the cell voltage being stable at ca.1.60 V.These results demonstrate that FeOOH/Cr-NiCo2O4/NF possesses an OWS performance superior to most of transition-metal based bifunctional electrocatalysts working in alkaline medium.The excellent bifunctional activity and stability of FeOOH/Cr-NiCo2O4/NF are attributed to the following reasons:(i)The NN structure provides a large specific surface area;(ii)the high conductivity of Cr-NiCo2O4 enables more active centers on the far-end part of NNs to be electrochemically reached;(iii)the deposition of FeOOH supplies additional active sites for OWS.
基金financial support from the National Natural Science Foundation of China(No.21376257)the Jiangsu Provincial Natural Science Foundation of China(No.BK20131112)
文摘To develop more ideal bifunctional heteroatom-doped carbon electrocatalysts toward the oxygen reduction reaction(ORR) and oxygen evolution reaction(OER) for regenerative fuel cells and rechargeable metal–air batteries, herein, tobacco-derived N-containing ordered mesoporous carbon(N-OMC) electrocatalysts with different N species distributions are designed. Results indicate that the as-prepared N-OMC with more pyrrolic and pyridinic Ns exhibits much higher activities for the ORR and OER than N-OMC with more graphitic N in both acidic and alkaline media, suggesting that the increase of pyrrolic and pyridinic Ns favors the improvement of ORR and OER activities of the N-containing carbon catalysts, and showing a great potential for the designing of more effective, lower-cost ORR and OER bifunctional electrocatalysts for future regenerative fuel cells and rechargeable metal–air batteries.
基金supported by the National Natural Science Foundation of China(Nos.21673290,U1662103)Science Foundation of China University of Petroleum,Beijing(No.2462017YJRC027)the Strategic Cooperation Technology Projects of CNPC and CUPB(No.ZLZX2020-04)。
文摘The strategy of adopting cheap precursors or abundant resources,which can be obtained directly from nature,is a simple and excellent method of introducing accessible research into environmentally friendly development.Moreover,this is also an urgent requirement for the sustainable development of green technology.Herein,we introduce a simplistic and expandable method to prepare metal-free biomassderived nitrogen self-doped porous activation carbon(N-PAC) with large specific surface area(S_(BET)=1300.58 m^(2)/g).Moreover,the manufactural electrocatalysts exhibit prominent oxygen reduction reaction(ORR) performance in all PH values.As compared with the commercial Pt/C catalyst,the N-PAC/800 with a positive onset potential at 10 mA/cm^(2)(0.93 V),half-wave potential(0.87 V),and limiting current(6.34 mA/cm^(2)) bring to light excellent catalytic stability,selectivity,and much-enhanced methanol tolerance.Furthermore,the prepared electrocatalysts possess considerable hydrogen evolution reaction(HER) performance with a less onset potential of 0.218 V(acidic medium) and0.271 V(alkaline medium) respectively,which can show similar catalytic activity across the whole pH range.Such bifunctional electrocatalyst,with excellent electrocatalytic properties,resource-rich,low cost,and environmental-friendly,hold a promising application in energy conversion and reserve.