High gravimetric energy density, earth-abundance, and environmental friendliness of hydrogen sources have inspired the utilization of hydrogen fuel as a clean alternative to fossil fuels. Hydrogen evolution reaction ...High gravimetric energy density, earth-abundance, and environmental friendliness of hydrogen sources have inspired the utilization of hydrogen fuel as a clean alternative to fossil fuels. Hydrogen evolution reaction （HER）, a half reaction of water splitting, is crucial to the low-cost production of pure H2 fuels but necessitates the use of electrocatalysts to expedite reaction kinetics. Owing to the availability of low-cost oxygen evolution reaction （OER） catalysts for the counter electrode in alkaline media and the lack of low-cost OER catalysts in acidic media, researchers have focused on developing HER catalysts in alkaline media with high activity and stability. Nickel is well-known as an HER catalyst and continuous efforts have been undertaken to improve Ni-based catalysts as alkaline electrolyzers： In this review, we summarize earlier studies of HER activity and mechanism on Ni surfaces, along with recent progress in the optimization of the Ni-based catalysts using various modern techniques. Recently developed Ni-based HER catalysts are categorized according to their chemical nature, and the advantages as well as limitations of each category are discussed. Among all Ni-based catalysts, Ni-based alloys and Ni-based hetero-structure exhibit the most promising electrocatalytic activity and stability owing to the fine-tuning of their surface adsorption properties via a synergistic nearby element or domain. Finally, selected applications of the developed Ni-based HER catalysts are highlighted, such as water splitting, the chloralkali process, and microbial electrolysis cell.展开更多
With the goal of constructing a carbon‐free energy cycle,proton‐exchange membrane(PEM)water electrolysis is a promising technology that can be integrated effectively with renewable energy resources to produce high‐...With the goal of constructing a carbon‐free energy cycle,proton‐exchange membrane(PEM)water electrolysis is a promising technology that can be integrated effectively with renewable energy resources to produce high‐purity hydrogen.IrO2,as a commercial electrocatalyst for the anode side of a PEM water electrolyzer,can both overcome the high corrosion conditions and exhibit efficient catalytic performance.However,the high consumption of Ir species cannot meet the sustainable development and economic requirements of this technology.Accordingly,it is necessary to understand the OER catalytic mechanisms for Ir species,further designing new types of low‐iridium catalysts with high activity and stability to replace IrO2.In this review,we first summarize the related catalytic mechanisms of the acidic oxygen evolution reaction(OER),and then provide general methods for measuring the catalytic performance of materials.Second,we present the structural evolution results of crystalline IrO2 and amorphous IrOx using in situ characterization techniques under catalytic conditions to understand the common catalytic characteristics of the materials and the possible factors affecting the structural evolution characteristics.Furthermore,we focus on three types of common low‐iridium catalysts,including heteroatom‐doped IrO2(IrOx)‐based catalysts,perovskite‐type iridium‐based catalysts,and pyrochlore‐type iridium‐based catalysts,and try to correlate the structural features with the intrinsic catalytic performance of materials.Finally,at the end of the review,we present the unresolved problems and challenges in this field in an attempt to develop effective strategies to further balance the catalytic activity and stability of materials under acidic OER catalytic conditions.展开更多
As a promising technology that may solve global environmental challenges and enable intermittent renewable energy storage as well as zero-carbon-emission energy cycling, the carbon dioxide reduction reaction has been ...As a promising technology that may solve global environmental challenges and enable intermittent renewable energy storage as well as zero-carbon-emission energy cycling, the carbon dioxide reduction reaction has been extensively studied in the past several years. Beyond the fruitful progresses and innovations in catalysts, the system engineering-based research on the full carbon dioxide reduction reaction is urgently needed toward the industrial application. In this review, we summarize and discuss recent works on the innovations in the reactor architectures and optimizations based on system engineering in carbon dioxide reduction reaction. Some challenges and future trends in this field are further discussed, especially on the system engineering factors.展开更多
Electro-oxidation of Ce （ Ⅲ ） to Ce （ Ⅳ ） in parallel plate flow type electrolyzer divided with cation exchange membrane was carried out in nitric acid media at carbon felt anode under galvanostatic conditions. ...Electro-oxidation of Ce （ Ⅲ ） to Ce （ Ⅳ ） in parallel plate flow type electrolyzer divided with cation exchange membrane was carried out in nitric acid media at carbon felt anode under galvanostatic conditions. Carbon felt was used as an anode for its high specific surface area and high oxygen evolution overpotential. Pt coated Ti plates were used as cathode and anode current feeder. The oxidation of 1 mol· L^-1 Ce（ Ⅲ ） solution in 2 mol· L^- 1 HNO3 was proceeding with a high current efficiency （92%） until about 80% of Ce（ Ⅲ ） was oxidized. Then, oxygen evolution, accompanied by terminal voltage jump, took place, lowering current efficiency. Ce（ Ⅲ ） was oxidized up to 90% with current efficiency of 62%. In this mode, strong carbon felt anode oxidation was observed. The wear out of carbon felt was 46% in six consequent runs （6 h of operation）. After each run, carbon felt surface had to be renewed with slightly alkaline solution to remove carbon oxidation products and ensure regular operational conditions. When anode surface was blocked, oxygen evolution took place from the beginning of electrolysis due to higher actual current density. The wear out of carbon felt anode could be minimized by means of oxygen evolution prevention. In the case when electrolysis had been stopped before oxygen evolution started （at Ce（ Ⅳ ） conversion of about 80% ）, the wear out of anode was less than 2% during 6 consequent runs （4 h of operation）.展开更多
文摘High gravimetric energy density, earth-abundance, and environmental friendliness of hydrogen sources have inspired the utilization of hydrogen fuel as a clean alternative to fossil fuels. Hydrogen evolution reaction （HER）, a half reaction of water splitting, is crucial to the low-cost production of pure H2 fuels but necessitates the use of electrocatalysts to expedite reaction kinetics. Owing to the availability of low-cost oxygen evolution reaction （OER） catalysts for the counter electrode in alkaline media and the lack of low-cost OER catalysts in acidic media, researchers have focused on developing HER catalysts in alkaline media with high activity and stability. Nickel is well-known as an HER catalyst and continuous efforts have been undertaken to improve Ni-based catalysts as alkaline electrolyzers： In this review, we summarize earlier studies of HER activity and mechanism on Ni surfaces, along with recent progress in the optimization of the Ni-based catalysts using various modern techniques. Recently developed Ni-based HER catalysts are categorized according to their chemical nature, and the advantages as well as limitations of each category are discussed. Among all Ni-based catalysts, Ni-based alloys and Ni-based hetero-structure exhibit the most promising electrocatalytic activity and stability owing to the fine-tuning of their surface adsorption properties via a synergistic nearby element or domain. Finally, selected applications of the developed Ni-based HER catalysts are highlighted, such as water splitting, the chloralkali process, and microbial electrolysis cell.
文摘With the goal of constructing a carbon‐free energy cycle,proton‐exchange membrane(PEM)water electrolysis is a promising technology that can be integrated effectively with renewable energy resources to produce high‐purity hydrogen.IrO2,as a commercial electrocatalyst for the anode side of a PEM water electrolyzer,can both overcome the high corrosion conditions and exhibit efficient catalytic performance.However,the high consumption of Ir species cannot meet the sustainable development and economic requirements of this technology.Accordingly,it is necessary to understand the OER catalytic mechanisms for Ir species,further designing new types of low‐iridium catalysts with high activity and stability to replace IrO2.In this review,we first summarize the related catalytic mechanisms of the acidic oxygen evolution reaction(OER),and then provide general methods for measuring the catalytic performance of materials.Second,we present the structural evolution results of crystalline IrO2 and amorphous IrOx using in situ characterization techniques under catalytic conditions to understand the common catalytic characteristics of the materials and the possible factors affecting the structural evolution characteristics.Furthermore,we focus on three types of common low‐iridium catalysts,including heteroatom‐doped IrO2(IrOx)‐based catalysts,perovskite‐type iridium‐based catalysts,and pyrochlore‐type iridium‐based catalysts,and try to correlate the structural features with the intrinsic catalytic performance of materials.Finally,at the end of the review,we present the unresolved problems and challenges in this field in an attempt to develop effective strategies to further balance the catalytic activity and stability of materials under acidic OER catalytic conditions.
基金supported by the National Key Research and Development Program of China (2017YFA0206901,2018YFA0209401)the National Natural Science Foundation of China (21975051,21773036)+2 种基金the Science and Technology Commission of Shanghai Municipality (17JC1402000,19XD1420400)the Innovation Program of Shanghai Municipal Education Commission (2019-01-07-00-07-E00045)the Shanghai Shu-Guang Program (15SG01)
文摘As a promising technology that may solve global environmental challenges and enable intermittent renewable energy storage as well as zero-carbon-emission energy cycling, the carbon dioxide reduction reaction has been extensively studied in the past several years. Beyond the fruitful progresses and innovations in catalysts, the system engineering-based research on the full carbon dioxide reduction reaction is urgently needed toward the industrial application. In this review, we summarize and discuss recent works on the innovations in the reactor architectures and optimizations based on system engineering in carbon dioxide reduction reaction. Some challenges and future trends in this field are further discussed, especially on the system engineering factors.
文摘Electro-oxidation of Ce （ Ⅲ ） to Ce （ Ⅳ ） in parallel plate flow type electrolyzer divided with cation exchange membrane was carried out in nitric acid media at carbon felt anode under galvanostatic conditions. Carbon felt was used as an anode for its high specific surface area and high oxygen evolution overpotential. Pt coated Ti plates were used as cathode and anode current feeder. The oxidation of 1 mol· L^-1 Ce（ Ⅲ ） solution in 2 mol· L^- 1 HNO3 was proceeding with a high current efficiency （92%） until about 80% of Ce（ Ⅲ ） was oxidized. Then, oxygen evolution, accompanied by terminal voltage jump, took place, lowering current efficiency. Ce（ Ⅲ ） was oxidized up to 90% with current efficiency of 62%. In this mode, strong carbon felt anode oxidation was observed. The wear out of carbon felt was 46% in six consequent runs （6 h of operation）. After each run, carbon felt surface had to be renewed with slightly alkaline solution to remove carbon oxidation products and ensure regular operational conditions. When anode surface was blocked, oxygen evolution took place from the beginning of electrolysis due to higher actual current density. The wear out of carbon felt anode could be minimized by means of oxygen evolution prevention. In the case when electrolysis had been stopped before oxygen evolution started （at Ce（ Ⅳ ） conversion of about 80% ）, the wear out of anode was less than 2% during 6 consequent runs （4 h of operation）.
