Nickel-based materials,including metallic Ni and Ni oxide,have been widely studied in the exploration of non-precious-metal hydrogen electrocatalysts,but neither pure Ni nor NiO is ideal for the hydrogen evolution rea...Nickel-based materials,including metallic Ni and Ni oxide,have been widely studied in the exploration of non-precious-metal hydrogen electrocatalysts,but neither pure Ni nor NiO is ideal for the hydrogen evolution reaction(HER)and hydrogen oxidation reaction(HOR).In this paper,an oxygen insertion strategy was applied on nickel to regulate its hydrogen electrocatalytic performance,and the oxygen-inserted nickel catalyst was successfully obtained with the assistance of tungsten dioxide support(denoted as O-Ni/WO_(2)).The partial insertion of oxygen in Ni maintains the face-centered cubic arrangement of Ni atoms,simultaneously expanding the lattice and increasing the lattice spacing.Consequently,the adsorption strength of^(*)H and^(*)OH on Ni is optimized,thus resulting in superior electrocatalytic performance of0-Ni/WO_(2)in alkaline HER/HOR.The Tafel slope of O-Ni/WO_(2)@NF for HER is 56 mV dec^(-1),and the kinetic current density of O-Ni/WO_(2)for HOR reaches 4.85 mA cm^(-2),which is ahead of most currently reported catalysts.Our proposed strategy of inserting an appropriate amount of anions into the metal lattice could provide more possibilities for the design of high-performance catalysts.展开更多
The demand for efficient and environmentally-benign electrocatalysts that help availably harness the renewable energy resources is growing rapidly. In recent years, increasing insights into the design of water electro...The demand for efficient and environmentally-benign electrocatalysts that help availably harness the renewable energy resources is growing rapidly. In recent years, increasing insights into the design of water electrolysers, fuel cells, and metal–air batteries emerge in response to the need for developing sustainable energy carriers, in which the oxygen evolution reaction and the oxygen reduction reaction play key roles. However, both reactions suffer from sluggish kinetics that restricts the reactivity. Therefore, it is vital to probe into the structure of the catalysts to exploit high-performance bifunctional oxygen electrocatalysts. Spinel-type catalysts are a class of materials with advantages of versatility, low toxicity, low expense, high abundance, flexible ion arrangement, and multivalence structure. In this review, we afford a basic overview of spinel-type materials and then introduce the relevant theoretical principles for electrocatalytic activity, following that we shed light on the structure–property relationship strategies for spinel-type catalysts including electronic structure, microstructure, phase and composition regulation,and coupling with electrically conductive supports. We elaborate the relationship between structure and property, in order to provide some insights into the design of spinel-type bifunctional oxygen electrocatalysts.展开更多
Electrocatalytic oxygen reduction reaction (ORR) via two-electron pathway is a promising approach to decentralized and on-site hydrogen peroxide (H_(2)O_(2)) production beyond the traditional anthraquinone process.In ...Electrocatalytic oxygen reduction reaction (ORR) via two-electron pathway is a promising approach to decentralized and on-site hydrogen peroxide (H_(2)O_(2)) production beyond the traditional anthraquinone process.In recent years,electrochemical H_(2)O_(2) production in acidic media has attracted increasing attention owing to its stronger oxidizing capacity,superior stability,and higher compatibility with various applications.Here,recent advances of H_(2)O_(2) electrosynthesis in acidic media are summarized.Specifically,fundamental aspects of two-electron ORR mechanism are firstly presented with an emphasis on the pH effect on catalytic performance.Major categories of promising electrocatalysts are then reviewed,including noble-metal-based materials,non-noble-metal single-atom catalysts,non-noblemetal compounds,and metal-free carbon-based materials.The innovative development of electrochemical devices and in situ/on-site application of electrogenerated H_(2)O_(2) are also highlighted to bridge the gap between laboratory-scale fundamental research and practically relevant H_(2)O_(2) electrosynthesis.Finally,critical perspectives on present challenges and promising opportunities for future research are provided.展开更多
To satisfy the rapid development of gas-involving electrocatalysis(O2, CO2, N2, etc.), nanostructured electrocatalysts with favorably regulated electronic structure and surface nanostructures are urgently required. He...To satisfy the rapid development of gas-involving electrocatalysis(O2, CO2, N2, etc.), nanostructured electrocatalysts with favorably regulated electronic structure and surface nanostructures are urgently required. Herein, we highlighted a core-branch hydroxysulfide as a significantly enhanced oxygen evolution reaction electrocatalyst. This hydroxysulfide was facilely fabricated via a versatile interfacial reaction in S2- inorganic solution at room temperature for a designed period. The moderative growth kinetics contributed to the growth of interconnected hydroxysulfide nanosheets with high-sulfur contents on the hydroxide precursor substrates, resulting in a hierarchical nanostructure with multifunctional modifications, including regulated electronic structure, rapid electron highway, excellent accessibility, and facilitated mass transfer. Such synthetic methodology can be generalized and facilely governed by regulating the temperature, concentration, duration, and solvent for targeted nanostructures. Contributed to the favorably regulated electronic structure and surface nanostructure, the as-obtained core-branch Co2NiS2.4(OH)1.2 sample exhibits superior OER performance, with a remarkably low overpotential(279 m V required for 10.0 m A c^m-2), a low Tafel slope(52 m V dec^-1), and a favorable long-term stability. This work not only presents a promising nanostructured hydroxysulfide for excellent OER electrocatalysis, but also shed fresh lights on the further rational development of efficient electrocatalysts.展开更多
BACKGROUND Targeted therapy based on pathway analysis of hepatitis B-related hepatocellular carcinoma(HCC)may be a promising remedy.CASE SUMMARY The present case involved an advanced hepatocellular carcinoma(HCC)patie...BACKGROUND Targeted therapy based on pathway analysis of hepatitis B-related hepatocellular carcinoma(HCC)may be a promising remedy.CASE SUMMARY The present case involved an advanced hepatocellular carcinoma(HCC)patient who did not receive local regional therapy and was intolerant to sorafenib.Total RNA extracted from the patient’s tumor tissue was used to obtain the gene mutation profile.The c.3676A>T and c.4402A>T stop-gain mutations in adenomatous polyposis coli(APC)were the most prevalent(42.2%and 35.1%,respectively).MutationMapper analysis indicated that the functional domain of APC was lost in the two APC mutant genes.APC is a major suppressor of the Wnt signaling pathway.Thus,the Wnt pathway was exclusively activated due to APC dysfunction,as other elements of this pathway were not found to be mutated.Aspirin has been reported to suppress the Wnt pathway by inducingβ-catenin phosphorylation through the activation of glycogen synthase kinase 3 beta via cyclooxygenase-2 pathway inhibition.Therefore,aspirin was administered to the patient,which achieved four years of disease control.CONCLUSION Exclusive mutations of APC of all the Wnt pathway elements could be a therapeutic target in HCC,with aspirin as an effective treatment option.展开更多
Two-dimensional(2D)carbon nanostructures play a critical role in energy-related applications,but developing facile and efficient strategies to synthesize these kinds of nanostructures is extremely rare.Herein,ultrathi...Two-dimensional(2D)carbon nanostructures play a critical role in energy-related applications,but developing facile and efficient strategies to synthesize these kinds of nanostructures is extremely rare.Herein,ultrathin carbon nanoribbons(CNRibs),with a thickness of 2–6 nm and length over 100 nm,have been strategically fabricated via a one-step pyrolysis of one-dimensional(1D)metal–organic framework nanorods(MOF NRods).Manipulating the diameters of MOF NRods will result in the formation of porous carbon nanostructures in 1D or 2D morphologies.Functional CNRibs with N doping or metal active site immobilization have also been studied.The CNRibs decorated with iron nanoclusters and single atoms have been used as excellent catalysts for the oxygen reduction reaction under both alkaline and acidic conditions,as well as zinc–air batteries.This work gives deep insights into the structural evolution from 1D to 2D morphology,providing an efficient approach to fabricate low-dimensional nanomaterials with controllable morphologies and functionalities for electrochemical applications.展开更多
CONSPECTUS:Energy electrocatalysis is an essential part for the modern energy network serving as the core technique in many electrochemical energy devices such as batteries,fuel cells,electrolyzers,etc.Developing high...CONSPECTUS:Energy electrocatalysis is an essential part for the modern energy network serving as the core technique in many electrochemical energy devices such as batteries,fuel cells,electrolyzers,etc.Developing high-performance electrocatalysts,especially the pursuit for higher intrinsic electrocatalytic activity,is the eternal theme for high-efficiency energy electrocatalysis.Transition metal compounds are highly considered as promising highperformance electrocatalysts due to their facile fabrication,well-defined structure,and encouraging intrinsic activity.However,further promotion on intrinsic electrocatalytic activity of conventional transition metal compounds encounters an unavoidable bottleneck originated from the rigid homoanion structure with limited choice of anions.Facing the above issue,heteroanion substitution on pristine transition metal compounds has been proposed in some recent research.Their unique structure and properties that distinguish them from routine transition metal compounds have attracted wide attention to reveal distinct electronic structures,synthesis methodologies,and functions in energy electrocatalysis for future application.展开更多
基金financially supported by National Natural Science Foundation of China(No.22209049,22075102,22005120)Natural Science Foundation of Guangdong Province(No.2023A1515012804)Fundamental Research Funds for the Central Universities(No.2022ZYGXZR048)。
文摘Nickel-based materials,including metallic Ni and Ni oxide,have been widely studied in the exploration of non-precious-metal hydrogen electrocatalysts,but neither pure Ni nor NiO is ideal for the hydrogen evolution reaction(HER)and hydrogen oxidation reaction(HOR).In this paper,an oxygen insertion strategy was applied on nickel to regulate its hydrogen electrocatalytic performance,and the oxygen-inserted nickel catalyst was successfully obtained with the assistance of tungsten dioxide support(denoted as O-Ni/WO_(2)).The partial insertion of oxygen in Ni maintains the face-centered cubic arrangement of Ni atoms,simultaneously expanding the lattice and increasing the lattice spacing.Consequently,the adsorption strength of^(*)H and^(*)OH on Ni is optimized,thus resulting in superior electrocatalytic performance of0-Ni/WO_(2)in alkaline HER/HOR.The Tafel slope of O-Ni/WO_(2)@NF for HER is 56 mV dec^(-1),and the kinetic current density of O-Ni/WO_(2)for HOR reaches 4.85 mA cm^(-2),which is ahead of most currently reported catalysts.Our proposed strategy of inserting an appropriate amount of anions into the metal lattice could provide more possibilities for the design of high-performance catalysts.
基金supported by the Natural Scientific Foundation of China (21825501)National Key Research and Development Program (2016YFA0202500 and 2016YFA0200102)+1 种基金Australian Research Council (DP160103107, FT170100224)Tsinghua University Initiative Scientific Research Program。
文摘The demand for efficient and environmentally-benign electrocatalysts that help availably harness the renewable energy resources is growing rapidly. In recent years, increasing insights into the design of water electrolysers, fuel cells, and metal–air batteries emerge in response to the need for developing sustainable energy carriers, in which the oxygen evolution reaction and the oxygen reduction reaction play key roles. However, both reactions suffer from sluggish kinetics that restricts the reactivity. Therefore, it is vital to probe into the structure of the catalysts to exploit high-performance bifunctional oxygen electrocatalysts. Spinel-type catalysts are a class of materials with advantages of versatility, low toxicity, low expense, high abundance, flexible ion arrangement, and multivalence structure. In this review, we afford a basic overview of spinel-type materials and then introduce the relevant theoretical principles for electrocatalytic activity, following that we shed light on the structure–property relationship strategies for spinel-type catalysts including electronic structure, microstructure, phase and composition regulation,and coupling with electrically conductive supports. We elaborate the relationship between structure and property, in order to provide some insights into the design of spinel-type bifunctional oxygen electrocatalysts.
基金The University of Adelaide for Early Career Researcher Seed Funding(15128587)the University of Electronic Science and Technology of China(UESTC)for Startup funding(A1098531023601264)the National Natural Science Foundation of China(NSFC 22102018 and 52171201)。
文摘Electrocatalytic oxygen reduction reaction (ORR) via two-electron pathway is a promising approach to decentralized and on-site hydrogen peroxide (H_(2)O_(2)) production beyond the traditional anthraquinone process.In recent years,electrochemical H_(2)O_(2) production in acidic media has attracted increasing attention owing to its stronger oxidizing capacity,superior stability,and higher compatibility with various applications.Here,recent advances of H_(2)O_(2) electrosynthesis in acidic media are summarized.Specifically,fundamental aspects of two-electron ORR mechanism are firstly presented with an emphasis on the pH effect on catalytic performance.Major categories of promising electrocatalysts are then reviewed,including noble-metal-based materials,non-noble-metal single-atom catalysts,non-noblemetal compounds,and metal-free carbon-based materials.The innovative development of electrochemical devices and in situ/on-site application of electrogenerated H_(2)O_(2) are also highlighted to bridge the gap between laboratory-scale fundamental research and practically relevant H_(2)O_(2) electrosynthesis.Finally,critical perspectives on present challenges and promising opportunities for future research are provided.
基金supported by the National Key Research and Development Program(2016YFA0202500 and 2016YFA0200101)the Natural Scientific Foundation of China(21825501)
文摘To satisfy the rapid development of gas-involving electrocatalysis(O2, CO2, N2, etc.), nanostructured electrocatalysts with favorably regulated electronic structure and surface nanostructures are urgently required. Herein, we highlighted a core-branch hydroxysulfide as a significantly enhanced oxygen evolution reaction electrocatalyst. This hydroxysulfide was facilely fabricated via a versatile interfacial reaction in S2- inorganic solution at room temperature for a designed period. The moderative growth kinetics contributed to the growth of interconnected hydroxysulfide nanosheets with high-sulfur contents on the hydroxide precursor substrates, resulting in a hierarchical nanostructure with multifunctional modifications, including regulated electronic structure, rapid electron highway, excellent accessibility, and facilitated mass transfer. Such synthetic methodology can be generalized and facilely governed by regulating the temperature, concentration, duration, and solvent for targeted nanostructures. Contributed to the favorably regulated electronic structure and surface nanostructure, the as-obtained core-branch Co2NiS2.4(OH)1.2 sample exhibits superior OER performance, with a remarkably low overpotential(279 m V required for 10.0 m A c^m-2), a low Tafel slope(52 m V dec^-1), and a favorable long-term stability. This work not only presents a promising nanostructured hydroxysulfide for excellent OER electrocatalysis, but also shed fresh lights on the further rational development of efficient electrocatalysts.
基金Guangzhou Science and Technology Project,No.201904010461Major Talents Project of Guangdong Province,No.2019TQ05Y266.
文摘BACKGROUND Targeted therapy based on pathway analysis of hepatitis B-related hepatocellular carcinoma(HCC)may be a promising remedy.CASE SUMMARY The present case involved an advanced hepatocellular carcinoma(HCC)patient who did not receive local regional therapy and was intolerant to sorafenib.Total RNA extracted from the patient’s tumor tissue was used to obtain the gene mutation profile.The c.3676A>T and c.4402A>T stop-gain mutations in adenomatous polyposis coli(APC)were the most prevalent(42.2%and 35.1%,respectively).MutationMapper analysis indicated that the functional domain of APC was lost in the two APC mutant genes.APC is a major suppressor of the Wnt signaling pathway.Thus,the Wnt pathway was exclusively activated due to APC dysfunction,as other elements of this pathway were not found to be mutated.Aspirin has been reported to suppress the Wnt pathway by inducingβ-catenin phosphorylation through the activation of glycogen synthase kinase 3 beta via cyclooxygenase-2 pathway inhibition.Therefore,aspirin was administered to the patient,which achieved four years of disease control.CONCLUSION Exclusive mutations of APC of all the Wnt pathway elements could be a therapeutic target in HCC,with aspirin as an effective treatment option.
基金The authors are thankful to Dr.Takeyuki Uchida for microscopic measurements,and AIST and Guangdong-Hong Kong-Macao Joint Laboratory(grant no.2019B121205001)for financial support.
文摘Two-dimensional(2D)carbon nanostructures play a critical role in energy-related applications,but developing facile and efficient strategies to synthesize these kinds of nanostructures is extremely rare.Herein,ultrathin carbon nanoribbons(CNRibs),with a thickness of 2–6 nm and length over 100 nm,have been strategically fabricated via a one-step pyrolysis of one-dimensional(1D)metal–organic framework nanorods(MOF NRods).Manipulating the diameters of MOF NRods will result in the formation of porous carbon nanostructures in 1D or 2D morphologies.Functional CNRibs with N doping or metal active site immobilization have also been studied.The CNRibs decorated with iron nanoclusters and single atoms have been used as excellent catalysts for the oxygen reduction reaction under both alkaline and acidic conditions,as well as zinc–air batteries.This work gives deep insights into the structural evolution from 1D to 2D morphology,providing an efficient approach to fabricate low-dimensional nanomaterials with controllable morphologies and functionalities for electrochemical applications.
基金This work was supported by National Natural Science Foundation of China(21825501)the Tsinghua University Initiative Scientific Research Program.
文摘CONSPECTUS:Energy electrocatalysis is an essential part for the modern energy network serving as the core technique in many electrochemical energy devices such as batteries,fuel cells,electrolyzers,etc.Developing high-performance electrocatalysts,especially the pursuit for higher intrinsic electrocatalytic activity,is the eternal theme for high-efficiency energy electrocatalysis.Transition metal compounds are highly considered as promising highperformance electrocatalysts due to their facile fabrication,well-defined structure,and encouraging intrinsic activity.However,further promotion on intrinsic electrocatalytic activity of conventional transition metal compounds encounters an unavoidable bottleneck originated from the rigid homoanion structure with limited choice of anions.Facing the above issue,heteroanion substitution on pristine transition metal compounds has been proposed in some recent research.Their unique structure and properties that distinguish them from routine transition metal compounds have attracted wide attention to reveal distinct electronic structures,synthesis methodologies,and functions in energy electrocatalysis for future application.
