While alloying transition metal chalcogenides(TMCs)with other chalcogen elements can effectively improve their conductivity and electrochemical properties,the optimal alloying content is still uncertain.In this study,...While alloying transition metal chalcogenides(TMCs)with other chalcogen elements can effectively improve their conductivity and electrochemical properties,the optimal alloying content is still uncertain.In this study,we study the influence of dopant concentration on the chemical bonds in TMC and reveal the associated stepwise conversion reaction mechanism for potassium ion storage.According to density function theory calculations,appropriate S-doping in Co0.85Se(Co_(0.85)Se_(1-x)S_(x))can reduce the average length of Co-Co bonds because of the electronegativity variation,which is thermodynamically favourable to the phase transition reactions.The optimal Se/S ratio(x=0.12)for the conductivity has been obtained from experimental results.When assembled as an anode in potassium-ion batteries(PIBs),the sample with optimized Se/S ratio exhibits extraordinary electrochemical performance.The rate performance(229.2 mA h g^(-1)at 10 A g^(-1))is superior to the state-of-the-art results.When assembled with Prussian blue(PB)as a cathode,the pouch cell exhibits excellent performance,demonstrating its great potential for applications.Moreover,the stepwise K+storage mechanism caused by the coexistence of S and Se is revealed by in-situ X-ray diffraction and ex-situ transmission electron microscopy techniques.Hence,this work not only provides an effective strategy to enhance the electrochemical performance of transition metal chalcogenides but also reveals the underlying mechanism for the construction of advanced electrode materials.展开更多
Developing Earth-abundant,highly efficient,and anticorrosion electrocatalysts to boost the oxygen evolution reaction(OER),oxygen reduction reaction(ORR),and hydrogen evolution reaction(HER) for the Zn–air battery(ZAB...Developing Earth-abundant,highly efficient,and anticorrosion electrocatalysts to boost the oxygen evolution reaction(OER),oxygen reduction reaction(ORR),and hydrogen evolution reaction(HER) for the Zn–air battery(ZAB) and for overall water splitting is imperative.In this study,a novel process starting with Cu2O cubes was developed to fabricate hollow NixCo1-xSe nanocages as trifunctional electrocatalysts for the OER,ORR,and HER and a reasonable formation mechanism was proposed.The Ni0.2Co0.8Se nanocages exhibited higher OER activity than its counterparts with the low overpotential of 280 mV at 10 mA cm-2.It also outperformed the other samples in the HER test with a low overpotential of 73 mV at 10 mA cm-2.As an air–cathode of a self-assembled rechargeable ZAB,it exhibited good performance,such as an ultralong cycling lifetime of > 50 h,a high round-trip efficiency of 60.86%,and a high power density of 223.5 mW cm-2.For the application in self-made all-solid-state ZAB,it also demonstrated excellent performance with a power density of 41.03 mW cm-2 and an open-circuit voltage of 1.428 V.In addition,Ni0.2Co0.8Se nanocages had superior performance in a practical overall water splitting,in which only 1.592 V was needed to achieve a current density of 10 mA cm-2.These results show that hollow NixCo1-xSe nanocages with an optimized Ni-to-Co ratio are a promising cost-effective and high-efficiency electrocatalyst for ZABs and overall water splitting in alkaline solutions.展开更多
Despite the existence of plentiful photocatalyst heterojunctions,their separation efficiency and charge flow precision remain low on account of lacking interfacial modulation.Herein,through a defect-induced heterojunc...Despite the existence of plentiful photocatalyst heterojunctions,their separation efficiency and charge flow precision remain low on account of lacking interfacial modulation.Herein,through a defect-induced heterojunction constructing strategy,Ni4Mo alloys were in-situ grown on the unsaturated coordinated sulfur atoms of sulfur vacancies-rich ZCS(Sv-ZCS)via interfacial Ni-S covalent bonds.The experimental and theoretical results reveal that these unsaturated sulfur atoms induced by sulfur vacancies vastly facilitate to anchor more Ni-Mo nanoparticles and form abundant Ni-S covalent bonds,meanwhile,these sulfur vacancies could form dual internal electric field(IEF)and work with Ni-S covalent bonds as“Electron Bridge”to further accelerate photoelectrons transfer,as well as promote the activation of water molecules and the desorption of hydrogen proton.Accordingly,the optimized Ni_(4)Mo/Sv-ZCS composite achieves an improved photocatalytic hydrogen evolution(PHE)rate of 94.69 mmol h^(-1)g^(-1)without an evident decrease after 6 cycles of photocatalytic tests,which is 21.2 and 1.94 times higher than those of Pt/ZCS and Ni_(4)Mo/ZCS,respectively.This tactic opens a new way for optimizing Zn_(x)Cd_(1-x)S-based heterojunctions by constructing sulfur vacancies and covalent bonds as“Electron Bridge”to enhance the activity of PHE.展开更多
通过水热法合成了Co_(5)Ni_(1)O_(x)/碳布(CC)电催化剂,研究了其微观结构、析氧反应/析氢反应电催化性能和电解水性能,并与Co_(6)O_(x)/CC、Ni_(6)O_(x)/CC以及商业Ru O_(2)和Pt/C电催化剂进行对比。结果表明:Co_(5)Ni_(1)O_(x)/CC试样...通过水热法合成了Co_(5)Ni_(1)O_(x)/碳布(CC)电催化剂,研究了其微观结构、析氧反应/析氢反应电催化性能和电解水性能,并与Co_(6)O_(x)/CC、Ni_(6)O_(x)/CC以及商业Ru O_(2)和Pt/C电催化剂进行对比。结果表明:Co_(5)Ni_(1)O_(x)/CC试样中的Co_(5)Ni_(1)O_(x)纳米棒负载于碳布表面;在电流密度为10 m A·cm^(-2)时,Co_(5)Ni_(1)O_(x)/CC试样发生析氧反应的过电位为289 m V,明显低于Co_(6)O_(x)/CC试样、Ni_(6)O_(x)/CC试样和Ru O_(2)电催化剂(342,405,422 m V),发生析氢反应的过电位为200 m V,低于Co_(6)O_(x)/CC试样和Ni_(6)O_(x)/CC试样(252,364 m V),更接近Pt/C电催化剂(44 m V);Co_(5)Ni_(1)O_(x)/CC试样组装的电解水槽电压为1.69 V,低于分别由Co_(6)O_(x)/CC和Ni_(6)O_(x)/CC试样组装的电解水槽电压(1.78,1.85 V),与Ru O_(2)和Pt/C电催化剂分别作为阳极与阴极组装的电解水槽电压相近(1.70 V)。展开更多
基金financially supported by the Natural Science Foundation of Jiangsu Province of China(BK20211172)the Jiangsu Provincial Department of Science and Technology Innovation Support Program(BK20222004,BZ2022036)+1 种基金the National Natural Science Foundation of China(52002366,22075263)the Fundamental Research Funds for the Central Universities(WK2060000039)。
文摘While alloying transition metal chalcogenides(TMCs)with other chalcogen elements can effectively improve their conductivity and electrochemical properties,the optimal alloying content is still uncertain.In this study,we study the influence of dopant concentration on the chemical bonds in TMC and reveal the associated stepwise conversion reaction mechanism for potassium ion storage.According to density function theory calculations,appropriate S-doping in Co0.85Se(Co_(0.85)Se_(1-x)S_(x))can reduce the average length of Co-Co bonds because of the electronegativity variation,which is thermodynamically favourable to the phase transition reactions.The optimal Se/S ratio(x=0.12)for the conductivity has been obtained from experimental results.When assembled as an anode in potassium-ion batteries(PIBs),the sample with optimized Se/S ratio exhibits extraordinary electrochemical performance.The rate performance(229.2 mA h g^(-1)at 10 A g^(-1))is superior to the state-of-the-art results.When assembled with Prussian blue(PB)as a cathode,the pouch cell exhibits excellent performance,demonstrating its great potential for applications.Moreover,the stepwise K+storage mechanism caused by the coexistence of S and Se is revealed by in-situ X-ray diffraction and ex-situ transmission electron microscopy techniques.Hence,this work not only provides an effective strategy to enhance the electrochemical performance of transition metal chalcogenides but also reveals the underlying mechanism for the construction of advanced electrode materials.
基金the Guangzhou Science and Technology Plan Projects(No.201804010323)the Guangdong Natural Science Funds for Distinguished Young Scholars(No.2015A030306006)+3 种基金the Guangdong Innovative and Entrepreneurial Research Team Program(No.2014ZT05N200)the Fundamental Research Funds for the Central Universities(SCUT Grant No.2018ZD022)the Project for Natural Science Foundation of Guangdong Province(No.2018A030313178)the funding support from the Natural Science Foundation of Guangdong Province(No.2015A030310176)
文摘Developing Earth-abundant,highly efficient,and anticorrosion electrocatalysts to boost the oxygen evolution reaction(OER),oxygen reduction reaction(ORR),and hydrogen evolution reaction(HER) for the Zn–air battery(ZAB) and for overall water splitting is imperative.In this study,a novel process starting with Cu2O cubes was developed to fabricate hollow NixCo1-xSe nanocages as trifunctional electrocatalysts for the OER,ORR,and HER and a reasonable formation mechanism was proposed.The Ni0.2Co0.8Se nanocages exhibited higher OER activity than its counterparts with the low overpotential of 280 mV at 10 mA cm-2.It also outperformed the other samples in the HER test with a low overpotential of 73 mV at 10 mA cm-2.As an air–cathode of a self-assembled rechargeable ZAB,it exhibited good performance,such as an ultralong cycling lifetime of > 50 h,a high round-trip efficiency of 60.86%,and a high power density of 223.5 mW cm-2.For the application in self-made all-solid-state ZAB,it also demonstrated excellent performance with a power density of 41.03 mW cm-2 and an open-circuit voltage of 1.428 V.In addition,Ni0.2Co0.8Se nanocages had superior performance in a practical overall water splitting,in which only 1.592 V was needed to achieve a current density of 10 mA cm-2.These results show that hollow NixCo1-xSe nanocages with an optimized Ni-to-Co ratio are a promising cost-effective and high-efficiency electrocatalyst for ZABs and overall water splitting in alkaline solutions.
基金supported by the National Natural Science Foundation of China under Grant(51871078 and 52071119)the Fundamental Research Funds for the Central Universities(HIT.OCEF.2021025)Open Project of State Key Laboratory of Urban Water Resource and Environment,Harbin Institute of Technology(ES202211)。
文摘Despite the existence of plentiful photocatalyst heterojunctions,their separation efficiency and charge flow precision remain low on account of lacking interfacial modulation.Herein,through a defect-induced heterojunction constructing strategy,Ni4Mo alloys were in-situ grown on the unsaturated coordinated sulfur atoms of sulfur vacancies-rich ZCS(Sv-ZCS)via interfacial Ni-S covalent bonds.The experimental and theoretical results reveal that these unsaturated sulfur atoms induced by sulfur vacancies vastly facilitate to anchor more Ni-Mo nanoparticles and form abundant Ni-S covalent bonds,meanwhile,these sulfur vacancies could form dual internal electric field(IEF)and work with Ni-S covalent bonds as“Electron Bridge”to further accelerate photoelectrons transfer,as well as promote the activation of water molecules and the desorption of hydrogen proton.Accordingly,the optimized Ni_(4)Mo/Sv-ZCS composite achieves an improved photocatalytic hydrogen evolution(PHE)rate of 94.69 mmol h^(-1)g^(-1)without an evident decrease after 6 cycles of photocatalytic tests,which is 21.2 and 1.94 times higher than those of Pt/ZCS and Ni_(4)Mo/ZCS,respectively.This tactic opens a new way for optimizing Zn_(x)Cd_(1-x)S-based heterojunctions by constructing sulfur vacancies and covalent bonds as“Electron Bridge”to enhance the activity of PHE.
文摘通过水热法合成了Co_(5)Ni_(1)O_(x)/碳布(CC)电催化剂,研究了其微观结构、析氧反应/析氢反应电催化性能和电解水性能,并与Co_(6)O_(x)/CC、Ni_(6)O_(x)/CC以及商业Ru O_(2)和Pt/C电催化剂进行对比。结果表明:Co_(5)Ni_(1)O_(x)/CC试样中的Co_(5)Ni_(1)O_(x)纳米棒负载于碳布表面;在电流密度为10 m A·cm^(-2)时,Co_(5)Ni_(1)O_(x)/CC试样发生析氧反应的过电位为289 m V,明显低于Co_(6)O_(x)/CC试样、Ni_(6)O_(x)/CC试样和Ru O_(2)电催化剂(342,405,422 m V),发生析氢反应的过电位为200 m V,低于Co_(6)O_(x)/CC试样和Ni_(6)O_(x)/CC试样(252,364 m V),更接近Pt/C电催化剂(44 m V);Co_(5)Ni_(1)O_(x)/CC试样组装的电解水槽电压为1.69 V,低于分别由Co_(6)O_(x)/CC和Ni_(6)O_(x)/CC试样组装的电解水槽电压(1.78,1.85 V),与Ru O_(2)和Pt/C电催化剂分别作为阳极与阴极组装的电解水槽电压相近(1.70 V)。
