The issues of fossil energy shortage and environmental pollution caused by the excessive consumption of conventional fossil fuels necessitates the exploration of renewable and clean energy sources such as hydrogen,whi...The issues of fossil energy shortage and environmental pollution caused by the excessive consumption of conventional fossil fuels necessitates the exploration of renewable and clean energy sources such as hydrogen,which is viable alternative to traditional energy sources in view of its high energy density and nonpolluting nature.In this regard,photocatalytic technology powered by inexhaustible solar energy is an ideal hydrogen production method.The recently developed copper-and zinc-based multinary metal sulfide(MMS)semiconductor photocatalysts exhibit the advantages of suitable bandgap,wide light-harvesting range,and flexible elemental composition,thus possessing great potential for achieving considerable photocatalytic hydrogen evolution(PHE)performance.Despite great progress has been achieved,the current photocatalysts still cannot meet the commercial application demands,which highlights the mechanisms understanding and optimization strategies for efficient PHE.Herein,the basic mechanisms of PHE,and effective optimization strategies are firstly introduced.Afterwards,the research process and the performance of copper-and zinc-based MMS photocatalysts,are thoroughly reviewed.Finally,the unresolved issues,and challenges hindering the achievement of overall water splitting have been discussed.展开更多
Thermoelectric（TE）materials have been considered as a strong candidate for recovering the waste heat from industry and vehicles due to the ability to convert heat directly into electricity.Recently,multinary diamond...Thermoelectric（TE）materials have been considered as a strong candidate for recovering the waste heat from industry and vehicles due to the ability to convert heat directly into electricity.Recently,multinary diamond-like chalcogenides（MDLCs）,such as Cu In Te2,Cu2Sn Se3,Cu3Sb Se4,Cu2ZnSnSe4,etc.,are eco-friendly Pb-free TE materials with relatively large Seebeck coefficient and low thermal conductivity and have aroused intensive research as a popular theme in the TE field.In this review,we summarize the TE performance and device development of MDLCs.The features of crystalline and electronic structure are first analyzed,and then the strategies that have emerged to enhance the TE figure of merits of these materials are illustrated in detail.The final part of this review describes the advance in TE device research for MDLCs.In the outlook,the challenges and future directions are also discussed to promote the further development of MDLCs TE materials.展开更多
Si is considered as the promising anode materials for lithium-ion batteries(LIBs)owing to their high capacities of 4200 mAh g-1and natural abundancy.However,severe electrode pulverization and poor electronic and Li-io...Si is considered as the promising anode materials for lithium-ion batteries(LIBs)owing to their high capacities of 4200 mAh g-1and natural abundancy.However,severe electrode pulverization and poor electronic and Li-ionic conductivities hinder their practical applications.To resolve the afore-mentioned problems,we first demonstrate a cation-mixed disordered lattice and unique Li storage mechanism of single-phase ternary GaSiP_(2)compound,where the liquid metallic Ga and highly reactive P are incorporated into Si through a ball milling method.As confirmed by experimental and theoretical analyses,the introduced Ga and P enables to achieve the stronger resistance against volume variation and metallic conductivity,respectively,while the cation-mixed lattice provides the faster Li-ionic diffusion capability than those of the parent GaP and Si phases.The resulting GaSiP_(2)electrodes delivered the high specific capacity of 1615 mAh g-1and high initial Coulombic efficiency of 91%,while the graphite-modified GaSiP_(2)(GaSiP_(2)@C)achieved 83%of capacity retention after 900 cycles and high-rate capacity of 800 at 10,000 mA g-1.Furthermore,the LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)//Ga SiP_(2)@C full cells achieved the high specific capacity of 1049 mAh g-1after 100 cycles,paving a way for the rational design of high-performance LIB anode materials.展开更多
Phosphides possess large reversible capacity, small voltage hysteresis, and high energy efficiency, thus promising to be new anode candidates to replace commercial graphite for Li-ion batteries(LIBs).Through a facile ...Phosphides possess large reversible capacity, small voltage hysteresis, and high energy efficiency, thus promising to be new anode candidates to replace commercial graphite for Li-ion batteries(LIBs).Through a facile mechanochemistry method, we prepare a novel ternary phosphide of Ga0.5Al0.5P whose crystalline structure is determined to be a cation-disordered cubic zinc sulfide structure according to XRD refinement. As an anode for LIBs, the Ga0.5Al0.5P delivers a reversible capacity of 1,352 mA h g^(-1)at100 mA g^(-1)with an initial Coulombic efficiency(ICE) up to 90.0% based on a reversible Li-storage mechanism integrating intercalation and subsequent conversion processes as confirmed by various characterizations techniques including in-situ XRD, ex-situ Raman, and XPS and electrochemical characterizations.Graphite-modified Ga0.5Al0.5P exhibits a long-lasting cycling stability of retaining 1,182 mA h g^(-1)after300 cycles at 100 m A g^(-1), and 625 mA h g^(-1)after 800 cycles at 2,000 mA g^(-1), and a high-rate performance of remaining 342 m A h g^(-1)at 20,000 mA g^(-1). The outstanding electrochemical performances can be attributed to enhanced reaction kinetics enabled by the capacitive behaviors and the faster Liion diffusion enabled by the cation-mixing. Importantly, by tuning the cationic ratio, we develop a novel series of cation-mixed compounds of Ga_(1/3)Al_(2/3)P, Ga_(1/4)Al_(3/4)P, Ga_(1/5)Al_(4/5)P, Ga_(2/3)Al_(1/3)P, Ga_(3/4)Al_(1/4)P, and Ga_(4/5)Al_(1/5)P, which demonstrate large capacity, high ICE, and suitable anode potentials. Broadly, these compounds with disordered lattices probably present novel physicochemical properties, and high electrochemical performances, thus providing a new perspective for new materials design.展开更多
Investigating enzymatic reaction in multimeric enzymes is utmost interest to improve our understanding of the mechanism of enzymatic reaction and regulation. In this study,
The development of single-component photocatalysts with narrow bandgaps(2.0-3.0 eV)has been one of the most important goals for photocatalytic H_(2)production,for which I-III-VI multinary sulfides play an important ro...The development of single-component photocatalysts with narrow bandgaps(2.0-3.0 eV)has been one of the most important goals for photocatalytic H_(2)production,for which I-III-VI multinary sulfides play an important role due to their widely tunable composition-dependent bandgap.However,simultaneous bandgap narrowing and photocatalytic activity enhancement in the I-III-VI sulfides are often difficult to achieve due to increased defect states.Here,a series of Cu-In-Zn-S quantum dots(QDs)were synthesized by a facile hydrothermal method focusing on a more profound understanding of bandgap tuning and the subsequent effect on the photocatalytic process by controlling the Cu content.The bandgap of the QDs can be effectively tuned from 2.90 eV to 1.98 eV with an increasing Cu:In ratio from 0.05:10 to 2.5:10 and a color change from light yellow to dark red.The QDs show photocatalytic H_(2)production activity even without any cocatalyst,but it quickly starts to decrease with the Cu/In ratio over 0.1:10(bandgap of 2.59 eV),which highly limits the potential for visible light photocatalysis.Interestingly,Pt-loading effectively enhanced not only the tolerance of Cu incorporation,but also enabled a high H_(2)production activity even with further bandgap narrowing down to~2 eV.The best photocatalytic performance of 456.4μmol h^(-1)g^(-1)was achieved for the Cu:In:Zn ratio of 1:10:5 with a bandgap of 2.27 eV.This increased tolerance of Cu content may result from a combined effect of charge separation by Pt as the cocatalyst that alleviated the Cu-induced charge recombination.The enhanced charge separation was proved by the photoluminescence quenching of the QDs with the cocatalyst.Electrochemical impedance spectroscopy was further used to study the charge separation properties of this photocatalytic system.This is the first observation of the cocatalyst-enhanced tolerance of Cu resulting from the competition of cocatalyst-induced charge separation and defect-induced charge recombination in multinary sulfides,which provides an interesting view and design guideline for the development of narrow bandgap photocatalysts.展开更多
文摘The issues of fossil energy shortage and environmental pollution caused by the excessive consumption of conventional fossil fuels necessitates the exploration of renewable and clean energy sources such as hydrogen,which is viable alternative to traditional energy sources in view of its high energy density and nonpolluting nature.In this regard,photocatalytic technology powered by inexhaustible solar energy is an ideal hydrogen production method.The recently developed copper-and zinc-based multinary metal sulfide(MMS)semiconductor photocatalysts exhibit the advantages of suitable bandgap,wide light-harvesting range,and flexible elemental composition,thus possessing great potential for achieving considerable photocatalytic hydrogen evolution(PHE)performance.Despite great progress has been achieved,the current photocatalysts still cannot meet the commercial application demands,which highlights the mechanisms understanding and optimization strategies for efficient PHE.Herein,the basic mechanisms of PHE,and effective optimization strategies are firstly introduced.Afterwards,the research process and the performance of copper-and zinc-based MMS photocatalysts,are thoroughly reviewed.Finally,the unresolved issues,and challenges hindering the achievement of overall water splitting have been discussed.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.51372064 and 61704044)the Key Project of the Natural Science Foundation of Hebei Province,China(Grant No.E2017201227)
文摘Thermoelectric（TE）materials have been considered as a strong candidate for recovering the waste heat from industry and vehicles due to the ability to convert heat directly into electricity.Recently,multinary diamond-like chalcogenides（MDLCs）,such as Cu In Te2,Cu2Sn Se3,Cu3Sb Se4,Cu2ZnSnSe4,etc.,are eco-friendly Pb-free TE materials with relatively large Seebeck coefficient and low thermal conductivity and have aroused intensive research as a popular theme in the TE field.In this review,we summarize the TE performance and device development of MDLCs.The features of crystalline and electronic structure are first analyzed,and then the strategies that have emerged to enhance the TE figure of merits of these materials are illustrated in detail.The final part of this review describes the advance in TE device research for MDLCs.In the outlook,the challenges and future directions are also discussed to promote the further development of MDLCs TE materials.
基金supported by National Natural Science Foundation of China(No.22178068)the Brain Pool(BP)program(No.2021H1D3A2A02045576)funded by National Research Foundation of KoreaNational Research Foundation of Korea grant funded by the Korea government(MSIT)(No.NRF-2020R1A3B2079803 and No.2021M3D1A2043791)。
文摘Si is considered as the promising anode materials for lithium-ion batteries(LIBs)owing to their high capacities of 4200 mAh g-1and natural abundancy.However,severe electrode pulverization and poor electronic and Li-ionic conductivities hinder their practical applications.To resolve the afore-mentioned problems,we first demonstrate a cation-mixed disordered lattice and unique Li storage mechanism of single-phase ternary GaSiP_(2)compound,where the liquid metallic Ga and highly reactive P are incorporated into Si through a ball milling method.As confirmed by experimental and theoretical analyses,the introduced Ga and P enables to achieve the stronger resistance against volume variation and metallic conductivity,respectively,while the cation-mixed lattice provides the faster Li-ionic diffusion capability than those of the parent GaP and Si phases.The resulting GaSiP_(2)electrodes delivered the high specific capacity of 1615 mAh g-1and high initial Coulombic efficiency of 91%,while the graphite-modified GaSiP_(2)(GaSiP_(2)@C)achieved 83%of capacity retention after 900 cycles and high-rate capacity of 800 at 10,000 mA g-1.Furthermore,the LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)//Ga SiP_(2)@C full cells achieved the high specific capacity of 1049 mAh g-1after 100 cycles,paving a way for the rational design of high-performance LIB anode materials.
基金supported by the National Natural Science Foundation of China (22178068)the Brain Pool program (2021H1D3A2A02045576) funded by National Research Foundation of Korea (NRF)。
文摘Phosphides possess large reversible capacity, small voltage hysteresis, and high energy efficiency, thus promising to be new anode candidates to replace commercial graphite for Li-ion batteries(LIBs).Through a facile mechanochemistry method, we prepare a novel ternary phosphide of Ga0.5Al0.5P whose crystalline structure is determined to be a cation-disordered cubic zinc sulfide structure according to XRD refinement. As an anode for LIBs, the Ga0.5Al0.5P delivers a reversible capacity of 1,352 mA h g^(-1)at100 mA g^(-1)with an initial Coulombic efficiency(ICE) up to 90.0% based on a reversible Li-storage mechanism integrating intercalation and subsequent conversion processes as confirmed by various characterizations techniques including in-situ XRD, ex-situ Raman, and XPS and electrochemical characterizations.Graphite-modified Ga0.5Al0.5P exhibits a long-lasting cycling stability of retaining 1,182 mA h g^(-1)after300 cycles at 100 m A g^(-1), and 625 mA h g^(-1)after 800 cycles at 2,000 mA g^(-1), and a high-rate performance of remaining 342 m A h g^(-1)at 20,000 mA g^(-1). The outstanding electrochemical performances can be attributed to enhanced reaction kinetics enabled by the capacitive behaviors and the faster Liion diffusion enabled by the cation-mixing. Importantly, by tuning the cationic ratio, we develop a novel series of cation-mixed compounds of Ga_(1/3)Al_(2/3)P, Ga_(1/4)Al_(3/4)P, Ga_(1/5)Al_(4/5)P, Ga_(2/3)Al_(1/3)P, Ga_(3/4)Al_(1/4)P, and Ga_(4/5)Al_(1/5)P, which demonstrate large capacity, high ICE, and suitable anode potentials. Broadly, these compounds with disordered lattices probably present novel physicochemical properties, and high electrochemical performances, thus providing a new perspective for new materials design.
文摘Investigating enzymatic reaction in multimeric enzymes is utmost interest to improve our understanding of the mechanism of enzymatic reaction and regulation. In this study,
基金support from the National Natural Science Foundation of China(21501072 and 21522603)the Jiangsu Specially-Appointed Professors Program,the Chinese-German Cooperation Research Project(GZ1091)+3 种基金the Natural Science Foundation of Jiangsu Province(BK20150489)the“Innovative and Entrepreneurial Doctor”Program of Jiangsu Province,the China Postdoctoral Science Foundation(2016M590419)the Jiangsu Province Postdoctoral Foundation(1501027A)the Start Funding of Jiangsu University(15JDG011 and 15JDG027).
文摘The development of single-component photocatalysts with narrow bandgaps(2.0-3.0 eV)has been one of the most important goals for photocatalytic H_(2)production,for which I-III-VI multinary sulfides play an important role due to their widely tunable composition-dependent bandgap.However,simultaneous bandgap narrowing and photocatalytic activity enhancement in the I-III-VI sulfides are often difficult to achieve due to increased defect states.Here,a series of Cu-In-Zn-S quantum dots(QDs)were synthesized by a facile hydrothermal method focusing on a more profound understanding of bandgap tuning and the subsequent effect on the photocatalytic process by controlling the Cu content.The bandgap of the QDs can be effectively tuned from 2.90 eV to 1.98 eV with an increasing Cu:In ratio from 0.05:10 to 2.5:10 and a color change from light yellow to dark red.The QDs show photocatalytic H_(2)production activity even without any cocatalyst,but it quickly starts to decrease with the Cu/In ratio over 0.1:10(bandgap of 2.59 eV),which highly limits the potential for visible light photocatalysis.Interestingly,Pt-loading effectively enhanced not only the tolerance of Cu incorporation,but also enabled a high H_(2)production activity even with further bandgap narrowing down to~2 eV.The best photocatalytic performance of 456.4μmol h^(-1)g^(-1)was achieved for the Cu:In:Zn ratio of 1:10:5 with a bandgap of 2.27 eV.This increased tolerance of Cu content may result from a combined effect of charge separation by Pt as the cocatalyst that alleviated the Cu-induced charge recombination.The enhanced charge separation was proved by the photoluminescence quenching of the QDs with the cocatalyst.Electrochemical impedance spectroscopy was further used to study the charge separation properties of this photocatalytic system.This is the first observation of the cocatalyst-enhanced tolerance of Cu resulting from the competition of cocatalyst-induced charge separation and defect-induced charge recombination in multinary sulfides,which provides an interesting view and design guideline for the development of narrow bandgap photocatalysts.
