Pub Date : 2024-11-01DOI: 10.3866/PKU.WHXB202311001
Peipei Sun , Jinyuan Zhang , Yanhua Song , Zhao Mo , Zhigang Chen , Hui Xu
The construct of the internal electric field (IEF) is recognized as an effective driver for promoting charge migration and separation to enhance photocatalytic performance. In this study, one-dimensional nanorods of Mn0.2Cd0.8S (MCS) co-doped with interstitial chlorine (Clint) and substitutional chlorine (Clsub) were designed and synthesized using a one-step solvothermal method. The incorporation of Clint and Clsub led to an unbalanced charge distribution and the formation of IEF in the MCS nanorods, contributing to the improvement of photogenerated carrier kinetic behavior. Through density functional theory (DFT) calculations, the effect of Clint and Clsub doping on the activity of the MCS was visually explained by examining differences in electronic structure, charge distribution and H2 adsorption/desorption balance. Interestingly, the modulation of the energy band structure of MCS primarily resulted from the contribution of Clint, while Clsub playing a negligible role. Moreover, the Clsub further facilitated the optimization of Clint concerning the H2 adsorption-desorption Gibbs free energy of MCS. Ultimately, the of 0.9 Cl-MCS favored H2 production (1.14 vs. 0.17 eV), leading to a 9 times increase in photocatalytic H2 production activity compared to MCS. This investigation presents a valuable approach for constructing IEF in bimetallic sulfide photocatalysts.
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{"title":"Built-in Electric Fields Enhancing Photocarrier Separation and H2 Evolution","authors":"Peipei Sun , Jinyuan Zhang , Yanhua Song , Zhao Mo , Zhigang Chen , Hui Xu","doi":"10.3866/PKU.WHXB202311001","DOIUrl":"10.3866/PKU.WHXB202311001","url":null,"abstract":"<div><div>The construct of the internal electric field (IEF) is recognized as an effective driver for promoting charge migration and separation to enhance photocatalytic performance. In this study, one-dimensional nanorods of Mn<sub>0.2</sub>Cd<sub>0.8</sub>S (MCS) co-doped with interstitial chlorine (Cl<sub>int</sub>) and substitutional chlorine (Cl<sub>sub</sub>) were designed and synthesized using a one-step solvothermal method. The incorporation of Cl<sub>int</sub> and Cl<sub>sub</sub> led to an unbalanced charge distribution and the formation of IEF in the MCS nanorods, contributing to the improvement of photogenerated carrier kinetic behavior. Through density functional theory (DFT) calculations, the effect of Cl<sub>int</sub> and Cl<sub>sub</sub> doping on the activity of the MCS was visually explained by examining differences in electronic structure, charge distribution and H<sub>2</sub> adsorption/desorption balance. Interestingly, the modulation of the energy band structure of MCS primarily resulted from the contribution of Cl<sub>int</sub>, while Cl<sub>sub</sub> playing a negligible role. Moreover, the Cl<sub>sub</sub> further facilitated the optimization of Cl<sub>int</sub> concerning the H<sub>2</sub> adsorption-desorption Gibbs free energy \u0000\t\t\t\t<span><math><mrow><mrow><mo>(</mo><mrow><mi>Δ</mi><msub><mi>G</mi><mrow><mtext>H</mtext><mo>*</mo></mrow></msub></mrow><mo>)</mo></mrow></mrow></math></span> of MCS. Ultimately, the \u0000\t\t\t\t<span><math><mrow><mi>Δ</mi><msub><mi>G</mi><mrow><mtext>H</mtext><mo>*</mo></mrow></msub></mrow></math></span> of 0.9 Cl-MCS favored H<sub>2</sub> production (1.14 <em>vs.</em> 0.17 eV), leading to a 9 times increase in photocatalytic H<sub>2</sub> production activity compared to MCS. This investigation presents a valuable approach for constructing IEF in bimetallic sulfide photocatalysts.</div><div><span><figure><span><img><ol><li><span><span>Download: <span>Download high-res image (91KB)</span></span></span></li><li><span><span>Download: <span>Download full-size image</span></span></span></li></ol></span></figure></span></div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"40 11","pages":"Article 2311001"},"PeriodicalIF":10.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143145012","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-01DOI: 10.3866/PKU.WHXB202311026
Xiaochen Zhang , Fei Yu , Jie Ma
<div><div>Capacitive deionization (CDI) technology is considered to be an emerging water treatment technology in the 21st century, owing to its low energy consumption, absence of secondary pollution, and straightforward operation. The advancement of basic theory and computer science has facilitated the use of multi-angle numerical simulations for CDI. However, due to errors in experimental methods, a direct understanding of mechanisms such as the kinetic characteristics of ion diffusion inside electrode materials, structural evolution during charging and discharging, and the intrinsic connection between potentials and structures is lacking. Existing experimental methods fall short of providing clear theoretical explanations for these phenomena. In contrast, numerical simulations offer a better comprehension of the chemical and electrochemical evolution in CDI. Beyond electrode materials, the device configuration of CDI significantly impacts its performance. Utilizing numerical simulations to study the optimal device configuration is expected to enhance economic efficiency and promote the practical application of CDI. While current reviews of CDI focus primarily on electrode materials and device configurations, there is a dearth of comprehensive reviews on cutting-edge numerical simulation research in the CDI field. This review commences with the earliest continuous-scale model used to describe the dynamic process of CDI. It systematically categorizes multi-angle numerical simulations in CDI, summarizes the strengths and weaknesses of different numerical simulation methods, and anticipates future development directions. Continuous-scale models accurately characterize the ion dynamics of CDI, determining rate and process constraints. Pore-scale models analyze the microstructure of porous media, obviating the need for empirical formulas to preset transport parameters for continuous-scale models. Researchers have introduced molecular dynamics simulation and density functional theory into CDI research, effectively analyzing the influence of structural features at the molecular/atomic level of electrode materials on the CDI system. This aids researchers in enhancing the efficacy and ionic selectivity of CDI electrode materials through pore engineering, defect engineering, and electrochemical microcosmic modulation engineering. Finite element analysis guides improvements in ion diffusion and stability of electrode materials, while computational fluid dynamics provides references for designing high-performance CDI devices. Data-driven machine learning excels in handling nonlinear data and uncovering complex mechanisms of CDI water treatment processes, while digital twin technology can reduce operation and maintenance costs of CDI. Considering costs in practical applications, techno-economic analysis plays a pivotal role in promoting the practical application of CDI technology. This review, the first of its kind, provides an essential theoretical foundati
{"title":"Cutting-Edge Applications of Multi-Angle Numerical Simulations for Capacitive Deionization","authors":"Xiaochen Zhang , Fei Yu , Jie Ma","doi":"10.3866/PKU.WHXB202311026","DOIUrl":"10.3866/PKU.WHXB202311026","url":null,"abstract":"<div><div>Capacitive deionization (CDI) technology is considered to be an emerging water treatment technology in the 21st century, owing to its low energy consumption, absence of secondary pollution, and straightforward operation. The advancement of basic theory and computer science has facilitated the use of multi-angle numerical simulations for CDI. However, due to errors in experimental methods, a direct understanding of mechanisms such as the kinetic characteristics of ion diffusion inside electrode materials, structural evolution during charging and discharging, and the intrinsic connection between potentials and structures is lacking. Existing experimental methods fall short of providing clear theoretical explanations for these phenomena. In contrast, numerical simulations offer a better comprehension of the chemical and electrochemical evolution in CDI. Beyond electrode materials, the device configuration of CDI significantly impacts its performance. Utilizing numerical simulations to study the optimal device configuration is expected to enhance economic efficiency and promote the practical application of CDI. While current reviews of CDI focus primarily on electrode materials and device configurations, there is a dearth of comprehensive reviews on cutting-edge numerical simulation research in the CDI field. This review commences with the earliest continuous-scale model used to describe the dynamic process of CDI. It systematically categorizes multi-angle numerical simulations in CDI, summarizes the strengths and weaknesses of different numerical simulation methods, and anticipates future development directions. Continuous-scale models accurately characterize the ion dynamics of CDI, determining rate and process constraints. Pore-scale models analyze the microstructure of porous media, obviating the need for empirical formulas to preset transport parameters for continuous-scale models. Researchers have introduced molecular dynamics simulation and density functional theory into CDI research, effectively analyzing the influence of structural features at the molecular/atomic level of electrode materials on the CDI system. This aids researchers in enhancing the efficacy and ionic selectivity of CDI electrode materials through pore engineering, defect engineering, and electrochemical microcosmic modulation engineering. Finite element analysis guides improvements in ion diffusion and stability of electrode materials, while computational fluid dynamics provides references for designing high-performance CDI devices. Data-driven machine learning excels in handling nonlinear data and uncovering complex mechanisms of CDI water treatment processes, while digital twin technology can reduce operation and maintenance costs of CDI. Considering costs in practical applications, techno-economic analysis plays a pivotal role in promoting the practical application of CDI technology. This review, the first of its kind, provides an essential theoretical foundati","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"40 11","pages":"Article 2311026"},"PeriodicalIF":10.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143145032","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-01DOI: 10.3866/PKU.WHXB202311011
Rui Li , Huan Liu , Yinan Jiao , Shengjian Qin , Jie Meng , Jiayu Song , Rongrong Yan , Hang Su , Hengbin Chen , Zixuan Shang , Jinjin Zhao
<div><div>Metal halide perovskite (MHP) materials show great prospects in applications such as solar cells, luminescent displays, and biomedicines, owing to their outstanding visible light absorption, photoelectric conversion, adjustable energy level structure, and low energy consumption. Their exceptional properties, such as high visible light absorption, efficient photoelectric conversion, adjustable energy level structure, and low energy consumption, have attracted significant attention. However, the presence of ion migration in MHPs has been identified as a critical challenge, leading to reduced energy conversion efficiency and device instability. Overcoming this obstacle is crucial for the commercialization of perovskite-based technologies. In recent years, extensive research has been conducted to understand the conditions and mechanisms of ion migration in perovskite materials, as well as develop strategies to mitigate its adverse effects. This paper adopts a dialectical perspective on ion migration, with a specific focus on energy barriers. A comprehensive review is provided, covering the fundamental concepts and formation mechanisms of both irreversible unidirectional and reversible bidirectional ion migrations. This paper begins by presenting a detailed summary of the degradation processes caused by irreversible unidirectional ion migrations phenomena induced by external fields, including illumination, stress/strain, thermal and electrical fields. Understanding the underlying mechanisms of such degradation is essential to address the stability concerns associated with perovskite devices. Moreover, the overview of bidirectional reversible ion migration phenomena in perovskite is presented. The cyclic formation and restoration of Schottky barriers at the interface can significantly influence the photoelectrical properties and impact the overall performance of perovskite devices. Various strategies for regulating ion migrations under external fields are discussed, aiming to enhance device stability and performance. By understanding the energy landscape and migration pathways, researchers can develop effective strategies to control and optimize ion migrations, ultimately improving the photoelectric conversion performance of perovskite devices. This paper provides comprehensive analysis of ion migration in perovskite materials, addressing fundamental concepts, ion migration mechanisms, and strategies for regulating ion migrations. By providing a clear understanding of the challenges associated with ion migration, this work contributes to the advancement of perovskite-based technologies and facilitates their commercialization. Ultimately, the optimization of ion migration control will lead to improved performance and stability of perovskite devices, enabling their widespread adoption in various applications.</div><div><span><figure><span><img><ol><li><span><span>Download: <span>Download high-res image (95KB)</span></span></span></li><li><span>
{"title":"Emerging Irreversible and Reversible Ion Migrations in Perovskites","authors":"Rui Li , Huan Liu , Yinan Jiao , Shengjian Qin , Jie Meng , Jiayu Song , Rongrong Yan , Hang Su , Hengbin Chen , Zixuan Shang , Jinjin Zhao","doi":"10.3866/PKU.WHXB202311011","DOIUrl":"10.3866/PKU.WHXB202311011","url":null,"abstract":"<div><div>Metal halide perovskite (MHP) materials show great prospects in applications such as solar cells, luminescent displays, and biomedicines, owing to their outstanding visible light absorption, photoelectric conversion, adjustable energy level structure, and low energy consumption. Their exceptional properties, such as high visible light absorption, efficient photoelectric conversion, adjustable energy level structure, and low energy consumption, have attracted significant attention. However, the presence of ion migration in MHPs has been identified as a critical challenge, leading to reduced energy conversion efficiency and device instability. Overcoming this obstacle is crucial for the commercialization of perovskite-based technologies. In recent years, extensive research has been conducted to understand the conditions and mechanisms of ion migration in perovskite materials, as well as develop strategies to mitigate its adverse effects. This paper adopts a dialectical perspective on ion migration, with a specific focus on energy barriers. A comprehensive review is provided, covering the fundamental concepts and formation mechanisms of both irreversible unidirectional and reversible bidirectional ion migrations. This paper begins by presenting a detailed summary of the degradation processes caused by irreversible unidirectional ion migrations phenomena induced by external fields, including illumination, stress/strain, thermal and electrical fields. Understanding the underlying mechanisms of such degradation is essential to address the stability concerns associated with perovskite devices. Moreover, the overview of bidirectional reversible ion migration phenomena in perovskite is presented. The cyclic formation and restoration of Schottky barriers at the interface can significantly influence the photoelectrical properties and impact the overall performance of perovskite devices. Various strategies for regulating ion migrations under external fields are discussed, aiming to enhance device stability and performance. By understanding the energy landscape and migration pathways, researchers can develop effective strategies to control and optimize ion migrations, ultimately improving the photoelectric conversion performance of perovskite devices. This paper provides comprehensive analysis of ion migration in perovskite materials, addressing fundamental concepts, ion migration mechanisms, and strategies for regulating ion migrations. By providing a clear understanding of the challenges associated with ion migration, this work contributes to the advancement of perovskite-based technologies and facilitates their commercialization. Ultimately, the optimization of ion migration control will lead to improved performance and stability of perovskite devices, enabling their widespread adoption in various applications.</div><div><span><figure><span><img><ol><li><span><span>Download: <span>Download high-res image (95KB)</span></span></span></li><li><span>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"40 11","pages":"Article 2311011"},"PeriodicalIF":10.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143145033","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-01DOI: 10.3866/PKU.WHXB202406019
Heng Chen, Longhui Nie, Kai Xu, Yiqiong Yang, Caihong Fang
The generation of hydrogen peroxide (H2O2) from water and oxygen redox reaction by photocatalysis has acquired increasing attention owing to its green and clean properties. Aiming at the low intrinsic photocatalytic activity of carbon nitride (g-C3N4), here, an ultrathin g-C3N4 nanosheet photocatalyst with a large surface area and enhanced crystallinity was fabricated by a two-step thermal polymerization technique. The calcination parameters showed a significant impact on the structural properties and catalytic performance of g-C3N4. The remarkable H2O2 yield (3177.0 μmolꞏg−1ꞏh−1) of CN-T-1 (by two-step calcination, 1 °Cꞏmin−1 optimal heating rate) was 3.7 times that (858.6 μmolꞏg−1ꞏh−1) of CN-O-1 (by one-step calcination, 1 °Cꞏmin−1 heating rate) and higher than those of pure g-C3N4 in literature. Most of the H2O2 yield for CN-T-1 remained after five cycles, showing good stability. The enhanced catalytic performance of CN-T-1 than CN-O-1 is owing to its larger specific surface area, enhanced crystallinity, higher oxygen adsorption ability and photogenerated carrier separation efficiency, longer lifetime of carriers, and slightly larger bandgap (3.07 eV, +0.26 eV bigger than CN-O-1) with more positive valence band position owing to ultrathin layers. The radicals were verified to be the primary active species. A two-step single electron ORR pathway was confirmed for H2O2 production over CN-T-1.
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{"title":"Remarkable Photocatalytic H2O2 Production Efficiency over Ultrathin g-C3N4 Nanosheet with Large Surface Area and Enhanced Crystallinity by Two-Step Calcination","authors":"Heng Chen, Longhui Nie, Kai Xu, Yiqiong Yang, Caihong Fang","doi":"10.3866/PKU.WHXB202406019","DOIUrl":"10.3866/PKU.WHXB202406019","url":null,"abstract":"<div><div>The generation of hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) from water and oxygen redox reaction by photocatalysis has acquired increasing attention owing to its green and clean properties. Aiming at the low intrinsic photocatalytic activity of carbon nitride (g-C<sub>3</sub>N<sub>4</sub>), here, an ultrathin g-C<sub>3</sub>N<sub>4</sub> nanosheet photocatalyst with a large surface area and enhanced crystallinity was fabricated by a two-step thermal polymerization technique. The calcination parameters showed a significant impact on the structural properties and catalytic performance of g-C<sub>3</sub>N<sub>4</sub>. The remarkable H<sub>2</sub>O<sub>2</sub> yield (3177.0 μmolꞏg<sup>−1</sup>ꞏh<sup>−1</sup>) of CN-T-1 (by two-step calcination, 1 °Cꞏmin<sup>−1</sup> optimal heating rate) was 3.7 times that (858.6 μmolꞏg<sup>−1</sup>ꞏh<sup>−1</sup>) of CN-O-1 (by one-step calcination, 1 °Cꞏmin<sup>−1</sup> heating rate) and higher than those of pure g-C<sub>3</sub>N<sub>4</sub> in literature. Most of the H<sub>2</sub>O<sub>2</sub> yield for CN-T-1 remained after five cycles, showing good stability. The enhanced catalytic performance of CN-T-1 than CN-O-1 is owing to its larger specific surface area, enhanced crystallinity, higher oxygen adsorption ability and photogenerated carrier separation efficiency, longer lifetime of carriers, and slightly larger bandgap (3.07 eV, +0.26 eV bigger than CN-O-1) with more positive valence band position owing to ultrathin layers. The \u0000\t\t\t\t<span><math><mrow><mo>⋅</mo><msubsup><mtext>O</mtext><mn>2</mn><mo>-</mo></msubsup></mrow></math></span> radicals were verified to be the primary active species. A two-step single electron ORR pathway \u0000\t\t\t\t<span><math><mrow><mo>(</mo><msub><mtext>O</mtext><mn>2</mn></msub><mo>+</mo><msup><mtext>e</mtext><mo>-</mo></msup><mo>→</mo><mo>⋅</mo><msubsup><mtext>O</mtext><mn>2</mn><mo>-</mo></msubsup><mo>→</mo><msub><mtext>H</mtext><mn>2</mn></msub><msub><mtext>O</mtext><mn>2</mn></msub><mo>)</mo></mrow></math></span> was confirmed for H<sub>2</sub>O<sub>2</sub> production over CN-T-1.</div><div><span><figure><span><img><ol><li><span><span>Download: <span>Download high-res image (107KB)</span></span></span></li><li><span><span>Download: <span>Download full-size image</span></span></span></li></ol></span></figure></span></div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"40 11","pages":"Article 2406019"},"PeriodicalIF":10.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143145959","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-01DOI: 10.3866/PKU.WHXB202403032
Yangrui Xu , Yewei Ren , Xinlin Liu , Hongping Li , Ziyang Lu
Increasing the CO2 concentration on the surface of the photocatalysts helps to increase the reaction dynamic rate of the photocatalytic CO2 reduction. However, the low solubility and poor mass transfer of CO2 in aqueous phase seriously hinder the adsorption and conversion of CO2 at the active site. In this work, the porous liquid photocatalyst (NH2-UIO-66 PL) with strong hydrophobicity has been synthesized by grafting the hydrophobic liquid end long-chain (PDMS) onto the amino site of metal-organic framework (NH2-UIO-66). It is found that the NH2-UIO-66 PL with permanent porosity causes a large amount of CO2 to be concentrated in the porous liquid cavity for transporting and diffusing CO2 onto the photocatalyst surface rapidly, and then the CO2 affinity surface with high positive potential and key intermediates for activation reduction reactions are formed with the grafting of hydrophobic PDMS, leading to stronger electron enrichment Zr active sites for enhancement of the overall CO2 reduction ability. As a result, NH2-UIO-66 PL achieved CO2 photoreduction with a CO yield of 24.70 μmol∙g−1∙h−1 and CH4 yield of 7.93 μmol∙g−1∙h−1, which is 2.3-fold and 2.7-fold compared to hydrophilic NH2-UIO-66, respectively. This research provides a novel design of hydrophobic porous liquids to provide industrial possibilities for high CO2 adsorption and reduction.
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{"title":"NH2-UIO-66 Based Hydrophobic Porous Liquid with High Mass Transfer and Affinity Surface for Enhancing CO2 Photoreduction","authors":"Yangrui Xu , Yewei Ren , Xinlin Liu , Hongping Li , Ziyang Lu","doi":"10.3866/PKU.WHXB202403032","DOIUrl":"10.3866/PKU.WHXB202403032","url":null,"abstract":"<div><div>Increasing the CO<sub>2</sub> concentration on the surface of the photocatalysts helps to increase the reaction dynamic rate of the photocatalytic CO<sub>2</sub> reduction. However, the low solubility and poor mass transfer of CO<sub>2</sub> in aqueous phase seriously hinder the adsorption and conversion of CO<sub>2</sub> at the active site. In this work, the porous liquid photocatalyst (NH<sub>2</sub>-UIO-66 PL) with strong hydrophobicity has been synthesized by grafting the hydrophobic liquid end long-chain (PDMS) onto the amino site of metal-organic framework (NH<sub>2</sub>-UIO-66). It is found that the NH<sub>2</sub>-UIO-66 PL with permanent porosity causes a large amount of CO<sub>2</sub> to be concentrated in the porous liquid cavity for transporting and diffusing CO<sub>2</sub> onto the photocatalyst surface rapidly, and then the CO<sub>2</sub> affinity surface with high positive potential and key intermediates for activation reduction reactions are formed with the grafting of hydrophobic PDMS, leading to stronger electron enrichment Zr active sites for enhancement of the overall CO<sub>2</sub> reduction ability. As a result, NH<sub>2</sub>-UIO-66 PL achieved CO<sub>2</sub> photoreduction with a CO yield of 24.70 μmol∙g<sup>−1</sup>∙h<sup>−1</sup> and CH<sub>4</sub> yield of 7.93 μmol∙g<sup>−1</sup>∙h<sup>−1</sup>, which is 2.3-fold and 2.7-fold compared to hydrophilic NH<sub>2</sub>-UIO-66, respectively. This research provides a novel design of hydrophobic porous liquids to provide industrial possibilities for high CO<sub>2</sub> adsorption and reduction.</div><div><span><figure><span><img><ol><li><span><span>Download: <span>Download high-res image (157KB)</span></span></span></li><li><span><span>Download: <span>Download full-size image</span></span></span></li></ol></span></figure></span></div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"40 11","pages":"Article 2403032"},"PeriodicalIF":10.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143145962","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-01DOI: 10.3866/PKU.WHXB202310034
Doudou Qin , Junyang Ding , Chu Liang , Qian Liu , Ligang Feng , Yang Luo , Guangzhi Hu , Jun Luo , Xijun Liu
<div><div>Non-renewable energy sources such as fossil fuels are increasingly depleted. In order to cope with the potential energy crisis, it is urgent to develop clean and efficient renewable energy sources. Advanced energy storage technology based on electrical energy holds critical significance to the sustainable and steady development of human society. Aqueous rechargeable batteries are a kind of promising electrochemical energy storage devices. Zinc-ion batteries (ZIBs) are gaining increasing popularity due to their safety, sustainability, cost-effectiveness and high energy density, positioning them as potential successors to current Lithium-ion batteries (LIBs) with a high degree of commercialization. The extraordinary mechanical flexibility and excellent electrochemical performance exhibited by ZIBs holds great significance in advancing the development of flexible and wearable batteries. Manganese-based oxides with large channel size possess the characteristics of high theoretical capacity, various oxidation states (including +2, +3, +4) and low cost, which are commonly employed as cathode materials for AZIBs. Nevertheless, the electrochemical performance of current manganese-based ZIBs is not satisfactory, facing the challenges of metal dissolution, material structure instability, notably a strong electrostatic interaction exhibited by divalent Zn<sup>2+</sup> ions in the host structure resulting in slow transmission kinetics. These challenges contribute to low cycle stability of the battery, impeding practical application and the progression of ZIBs. To solve these problems, diverse structural engineering strategies including defect engineering have been exploited, which can effectively improve the transport kinetics of zinc ions. From the perspective of enhancing the performance of the material itself, interlayer intercalation and other measures can be taken to better the microstructure or morphology of manganese-based materials. By improving the electrical conductivity of the material and enhancing ionic bonding, the structural stability and electrochemical performance of the material can be effectively improved. And from the angle of battery design, in order to improve the stability of the electrode-electrolyte interface, the electrolyte is optimized, or a fresh preparation method different from the conventional slurry coating process is adopted, which is also a promising method to design a new electrode without binder and the electrode components can still be evenly distributed. This review provides an overview of Zinc-ion storage mechanisms: the reversible Zn<sup>2+</sup> insertion/extraction; the reversible interposition and deintercalation of Zn<sup>2+</sup> and H<sup>+</sup>; the chemical conversion reactions, and the mechanism of dissolution-deposition reaction. Furthermore, the challenges faced by manganese-based cathode materials are clarified, and the optimization strategies to improve their electrochemical performance by incr
{"title":"Addressing Challenges and Enhancing Performance of Manganese-based Cathode Materials in Aqueous Zinc-Ion Batteries","authors":"Doudou Qin , Junyang Ding , Chu Liang , Qian Liu , Ligang Feng , Yang Luo , Guangzhi Hu , Jun Luo , Xijun Liu","doi":"10.3866/PKU.WHXB202310034","DOIUrl":"10.3866/PKU.WHXB202310034","url":null,"abstract":"<div><div>Non-renewable energy sources such as fossil fuels are increasingly depleted. In order to cope with the potential energy crisis, it is urgent to develop clean and efficient renewable energy sources. Advanced energy storage technology based on electrical energy holds critical significance to the sustainable and steady development of human society. Aqueous rechargeable batteries are a kind of promising electrochemical energy storage devices. Zinc-ion batteries (ZIBs) are gaining increasing popularity due to their safety, sustainability, cost-effectiveness and high energy density, positioning them as potential successors to current Lithium-ion batteries (LIBs) with a high degree of commercialization. The extraordinary mechanical flexibility and excellent electrochemical performance exhibited by ZIBs holds great significance in advancing the development of flexible and wearable batteries. Manganese-based oxides with large channel size possess the characteristics of high theoretical capacity, various oxidation states (including +2, +3, +4) and low cost, which are commonly employed as cathode materials for AZIBs. Nevertheless, the electrochemical performance of current manganese-based ZIBs is not satisfactory, facing the challenges of metal dissolution, material structure instability, notably a strong electrostatic interaction exhibited by divalent Zn<sup>2+</sup> ions in the host structure resulting in slow transmission kinetics. These challenges contribute to low cycle stability of the battery, impeding practical application and the progression of ZIBs. To solve these problems, diverse structural engineering strategies including defect engineering have been exploited, which can effectively improve the transport kinetics of zinc ions. From the perspective of enhancing the performance of the material itself, interlayer intercalation and other measures can be taken to better the microstructure or morphology of manganese-based materials. By improving the electrical conductivity of the material and enhancing ionic bonding, the structural stability and electrochemical performance of the material can be effectively improved. And from the angle of battery design, in order to improve the stability of the electrode-electrolyte interface, the electrolyte is optimized, or a fresh preparation method different from the conventional slurry coating process is adopted, which is also a promising method to design a new electrode without binder and the electrode components can still be evenly distributed. This review provides an overview of Zinc-ion storage mechanisms: the reversible Zn<sup>2+</sup> insertion/extraction; the reversible interposition and deintercalation of Zn<sup>2+</sup> and H<sup>+</sup>; the chemical conversion reactions, and the mechanism of dissolution-deposition reaction. Furthermore, the challenges faced by manganese-based cathode materials are clarified, and the optimization strategies to improve their electrochemical performance by incr","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"40 10","pages":"Article 2310034"},"PeriodicalIF":10.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143155713","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-01DOI: 10.3866/PKU.WHXB202311016
Qianqian Liu , Xing Du , Wanfei Li , Wei-Lin Dai , Bo Liu
Directional electron transfer is an appealing strategy for harnessing photogenerated charge separation kinetics. Herein, a novel 2D/1D SnNb2O6/nitrogen-enriched C3N5 S-scheme heterojunction with strong internal electric field (IEF) and dipole field (DF) is designed through in situ growth of C3N5 nanorods on SnNb2O6 nanosheets. The IEF generated at the interface via the formation of the S-scheme heterojunction induces directional charge transfer from SnNb2O6 to C3N5. Simultaneously, the DF within C3N5 provides the impetus to guide photo-excited electrons to the active sites. Consequently, the synergistic effects of IEF and DF facilitate swift directional electron transfer. The optimized SnNb2O6/C3N5 heterojunction demonstrates a remarkable H2 production rate of 1090.0 μmol∙g−1∙h−1 with continuous release of H2 bubbles. This performance surpasses that of SnNb2O6 and C3N5 by 38.8 and 10.7 times, respectively. Additionally, the SnNb2O6/C3N5 heterojunction exhibits superior activity in the removal of Rhodamine B, tetracycline, and Cr(VI). Based on electron paramagnetic resonance (EPR), time-resolved photoluminescence (TPRL) and density functional theory (DFT) calculations, etc., the directional charge transfer mechanism was systematically explored. The research furnishes a plausible approach to construct effective heterojunction photocatalysts for applications in energy and environmental domains.
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{"title":"Synergistic Effects of Internal Electric and Dipole Fields in SnNb2O6/Nitrogen-Enriched C3N5 S-Scheme Heterojunction for Boosting Photocatalytic Performance","authors":"Qianqian Liu , Xing Du , Wanfei Li , Wei-Lin Dai , Bo Liu","doi":"10.3866/PKU.WHXB202311016","DOIUrl":"10.3866/PKU.WHXB202311016","url":null,"abstract":"<div><div>Directional electron transfer is an appealing strategy for harnessing photogenerated charge separation kinetics. Herein, a novel 2D/1D SnNb<sub>2</sub>O<sub>6</sub>/nitrogen-enriched C<sub>3</sub>N<sub>5</sub> S-scheme heterojunction with strong internal electric field (IEF) and dipole field (DF) is designed through <em>in situ</em> growth of C<sub>3</sub>N<sub>5</sub> nanorods on SnNb<sub>2</sub>O<sub>6</sub> nanosheets. The IEF generated at the interface <em>via</em> the formation of the S-scheme heterojunction induces directional charge transfer from SnNb<sub>2</sub>O<sub>6</sub> to C<sub>3</sub>N<sub>5</sub>. Simultaneously, the DF within C<sub>3</sub>N<sub>5</sub> provides the impetus to guide photo-excited electrons to the active sites. Consequently, the synergistic effects of IEF and DF facilitate swift directional electron transfer. The optimized SnNb<sub>2</sub>O<sub>6</sub>/C<sub>3</sub>N<sub>5</sub> heterojunction demonstrates a remarkable H<sub>2</sub> production rate of 1090.0 μmol∙g<sup>−1</sup>∙h<sup>−1</sup> with continuous release of H<sub>2</sub> bubbles. This performance surpasses that of SnNb<sub>2</sub>O<sub>6</sub> and C<sub>3</sub>N<sub>5</sub> by 38.8 and 10.7 times, respectively. Additionally, the SnNb<sub>2</sub>O<sub>6</sub>/C<sub>3</sub>N<sub>5</sub> heterojunction exhibits superior activity in the removal of Rhodamine B, tetracycline, and Cr(VI). Based on electron paramagnetic resonance (EPR), time-resolved photoluminescence (TPRL) and density functional theory (DFT) calculations, <em>etc</em>., the directional charge transfer mechanism was systematically explored. The research furnishes a plausible approach to construct effective heterojunction photocatalysts for applications in energy and environmental domains.</div><div><span><figure><span><img><ol><li><span><span>Download: <span>Download high-res image (150KB)</span></span></span></li><li><span><span>Download: <span>Download full-size image</span></span></span></li></ol></span></figure></span></div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"40 10","pages":"Article 2311016"},"PeriodicalIF":10.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143099756","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-01DOI: 10.3866/PKU.WHXB202309031
Xiutao Xu , Chunfeng Shao , Jinfeng Zhang, Zhongliao Wang, Kai Dai
<div><div>In the pursuit of efficient photocatalytic carbon dioxide (CO<sub>2</sub>) conversion, the use of artificial semiconductors powered by solar energy offers great potential for simulating natural carbon cycling. However, the efficiency of photocatalytic CO<sub>2</sub> conversion remains suboptimal, primarily due to inadequate separation of photogenerated charges, which hinders the performance of semiconductor-based CO<sub>2</sub> reduction. Consequently, recent research efforts have focused on identifying ideal materials for CO<sub>2</sub> photocatalytic conversion. Among the candidate materials, the structure of Bi<sub>2</sub>MoO<sub>6</sub> consists of alternating layers of (Bi<sub>2</sub>O<sub>2</sub>)<sup>2+</sup> and perovskite-like (MoO<sub>4</sub>)<sup>2−</sup> layers with shared oxygen atoms between them. This inherent charge distribution within Bi<sub>2</sub>MoO<sub>6</sub> creates an inhomogeneous electric field, facilitating the efficient separation of photogenerated charge carriers. The morphology and structure of a catalyst significantly influence the rate of recombination of photogenerated charge carriers. Research has shown that ultrathin Bi<sub>2</sub>MoO<sub>6</sub> nanosheets, compared to other 2D and 3D structures of Bi<sub>2</sub>MoO<sub>6</sub> materials, possess longer fluorescence lifetimes, providing more opportunities for the separation of photogenerated charge carriers. However, Bi<sub>2</sub>MoO<sub>6</sub> still exhibits relatively low catalytic efficiency due to its insufficiently negative conduction band position (ranging between −0.2 and −0.4 V). To address this limitation, a viable strategy is to load a semiconductor with a more negatively positioned conduction band onto Bi<sub>2</sub>MoO<sub>6</sub>, creating an S-scheme heterojunction. In this study, Bi<sub>2</sub>MoO<sub>6</sub> nanosheets were synthesized through a hydrothermal method, and simultaneously, CeO<sub>2</sub> nanoparticles were grown on their surfaces, forming an S-scheme heterojunction modified with Ce<sup>3+</sup>/Ce<sup>4+</sup> ion bridges. Time-resolved photoluminescence (TRPL) and photoelectrochemical tests demonstrated the enhanced charge separation effect of this heterojunction. <em>In situ</em> X-ray photoelectron spectroscopy (<em>In situ</em> XPS) analysis and theoretical calculations further confirmed that photogenerated electrons follow an S-scheme mechanism, transferring from Bi<sub>2</sub>MoO<sub>6</sub> to CeO<sub>2</sub>. Experimental results revealed that the photocatalytic CO<sub>2</sub> reduction efficiencies of CeO<sub>2</sub>/Bi<sub>2</sub>MoO<sub>6</sub>, Bi<sub>2</sub>MoO<sub>6</sub>, and CeO<sub>2</sub> were 65.3, 14.8, and 1.2 μmol∙g<sup>−1</sup>∙h<sup>−1</sup>, respectively. Compared to pure Bi<sub>2</sub>MoO<sub>6</sub>, the catalytic efficiency of the CeO<sub>2</sub>/Bi<sub>2</sub>MoO<sub>6</sub> composite catalyst for CO<sub>2</sub> photocatalytic reduction to CO improved by a factor of 3.12. This enhancement in
{"title":"Rational Design of S-Scheme CeO2/Bi2MoO6 Microsphere Heterojunction for Efficient Photocatalytic CO2 Reduction","authors":"Xiutao Xu , Chunfeng Shao , Jinfeng Zhang, Zhongliao Wang, Kai Dai","doi":"10.3866/PKU.WHXB202309031","DOIUrl":"10.3866/PKU.WHXB202309031","url":null,"abstract":"<div><div>In the pursuit of efficient photocatalytic carbon dioxide (CO<sub>2</sub>) conversion, the use of artificial semiconductors powered by solar energy offers great potential for simulating natural carbon cycling. However, the efficiency of photocatalytic CO<sub>2</sub> conversion remains suboptimal, primarily due to inadequate separation of photogenerated charges, which hinders the performance of semiconductor-based CO<sub>2</sub> reduction. Consequently, recent research efforts have focused on identifying ideal materials for CO<sub>2</sub> photocatalytic conversion. Among the candidate materials, the structure of Bi<sub>2</sub>MoO<sub>6</sub> consists of alternating layers of (Bi<sub>2</sub>O<sub>2</sub>)<sup>2+</sup> and perovskite-like (MoO<sub>4</sub>)<sup>2−</sup> layers with shared oxygen atoms between them. This inherent charge distribution within Bi<sub>2</sub>MoO<sub>6</sub> creates an inhomogeneous electric field, facilitating the efficient separation of photogenerated charge carriers. The morphology and structure of a catalyst significantly influence the rate of recombination of photogenerated charge carriers. Research has shown that ultrathin Bi<sub>2</sub>MoO<sub>6</sub> nanosheets, compared to other 2D and 3D structures of Bi<sub>2</sub>MoO<sub>6</sub> materials, possess longer fluorescence lifetimes, providing more opportunities for the separation of photogenerated charge carriers. However, Bi<sub>2</sub>MoO<sub>6</sub> still exhibits relatively low catalytic efficiency due to its insufficiently negative conduction band position (ranging between −0.2 and −0.4 V). To address this limitation, a viable strategy is to load a semiconductor with a more negatively positioned conduction band onto Bi<sub>2</sub>MoO<sub>6</sub>, creating an S-scheme heterojunction. In this study, Bi<sub>2</sub>MoO<sub>6</sub> nanosheets were synthesized through a hydrothermal method, and simultaneously, CeO<sub>2</sub> nanoparticles were grown on their surfaces, forming an S-scheme heterojunction modified with Ce<sup>3+</sup>/Ce<sup>4+</sup> ion bridges. Time-resolved photoluminescence (TRPL) and photoelectrochemical tests demonstrated the enhanced charge separation effect of this heterojunction. <em>In situ</em> X-ray photoelectron spectroscopy (<em>In situ</em> XPS) analysis and theoretical calculations further confirmed that photogenerated electrons follow an S-scheme mechanism, transferring from Bi<sub>2</sub>MoO<sub>6</sub> to CeO<sub>2</sub>. Experimental results revealed that the photocatalytic CO<sub>2</sub> reduction efficiencies of CeO<sub>2</sub>/Bi<sub>2</sub>MoO<sub>6</sub>, Bi<sub>2</sub>MoO<sub>6</sub>, and CeO<sub>2</sub> were 65.3, 14.8, and 1.2 μmol∙g<sup>−1</sup>∙h<sup>−1</sup>, respectively. Compared to pure Bi<sub>2</sub>MoO<sub>6</sub>, the catalytic efficiency of the CeO<sub>2</sub>/Bi<sub>2</sub>MoO<sub>6</sub> composite catalyst for CO<sub>2</sub> photocatalytic reduction to CO improved by a factor of 3.12. This enhancement in","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"40 10","pages":"Article 2309031"},"PeriodicalIF":10.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143099718","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-01DOI: 10.3866/PKU.WHXB202309020
Tong Zhou , Xue Liu , Liang Zhao , Mingtao Qiao , Wanying Lei
<div><div>Artificial photosynthesis is an appealing approach for generating hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) from H<sub>2</sub>O and O<sub>2</sub> with solar energy as the sole energy input. However, the current catalyst systems commonly face challenges such as the limited optical absorption, poor electron-hole pair separation efficiency, and restricted surface reactivity, which hinders the overall photoactivity. Here, we immobilize cubic-phase ultrathin In<sub>4</sub>SnS<sub>8</sub> nanosheets (<em>E</em><sub>g</sub> = 2.16 eV) with thickness of 5–10 nm on the surface of few-layer Ti<sub>3</sub>C<sub>2</sub> to develop a sandwich-like hierarchical structure of Ti<sub>3</sub>C<sub>2</sub>/In<sub>4</sub>SnS<sub>8</sub> nanohybrid <em>via in situ</em> hydrothermal strategy. The enlarged interfacial area and close contact between Ti<sub>3</sub>C<sub>2</sub> and In<sub>4</sub>SnS<sub>8</sub> benefit for carrier transportation among nanohybrids. Characterization through X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) corroborates the successful construction of Ti<sub>3</sub>C<sub>2</sub>/In<sub>4</sub>SnS<sub>8</sub> nanostructures. Band structures investigation including valence band maximum and Mott-Schottky plots reveals the formation of Schottky junction in this 2D/2D heterostructure, that favors for ultrafast charge carrier separation and transportation from In<sub>4</sub>SnS<sub>8</sub> to Ti<sub>3</sub>C<sub>2</sub> and preventing the electrons backflow from Ti<sub>3</sub>C<sub>2</sub> to In<sub>4</sub>SnS<sub>8</sub>. Photoluminescene analysis and photo/electrochemical measurements prove that the combination of Ti<sub>3</sub>C<sub>2</sub> and In<sub>4</sub>SnS<sub>8</sub> accelerates the transportation of photoexcited electron-hole pairs and efficiently suppresses charge carrier recombination. Unsurprisingly, 7 wt% Ti<sub>3</sub>C<sub>2</sub>/In<sub>4</sub>SnS<sub>8</sub> catalysts exhibit the highest visible-light-driven photoreactivity with H<sub>2</sub>O<sub>2</sub> production rates of 1.998 μmol∙L<sup>−1</sup>∙min<sup>‒1</sup> that is 2.2 times larger than that of single In<sub>4</sub>SnS<sub>8</sub>. Additionally, Ti<sub>3</sub>C<sub>2</sub>/In<sub>4</sub>SnS<sub>8</sub> demonstrates a multifunctional capability in Cr(VI) reduction with the greatest reaction rates of 19.8 × 10<sup>−3</sup> min<sup>‒1</sup> that is almost 4-fold larger than that of individual semiconductor. Moreover, the nanohybrids exhibit excellent photostability after 5 cycles testing in both reaction systems. The morphology, crystal structure and composition for Ti<sub>3</sub>C<sub>2</sub>/In<sub>4</sub>SnS<sub>8</sub> remain unaltered after photoreaction. A comprehensive analysis including trapping agents and atmosphere experiments as well as electron paramagnetic resonance demonstrates that the H<sub>2</sub>O<sub>2</sub> evolution pathway consists of two channels: a two-step successive 1e<sup>‒
{"title":"Efficient Photocatalytic H2O2 Production and Cr(VI) Reduction over a Hierarchical Ti3C2/In4SnS8 Schottky Junction","authors":"Tong Zhou , Xue Liu , Liang Zhao , Mingtao Qiao , Wanying Lei","doi":"10.3866/PKU.WHXB202309020","DOIUrl":"10.3866/PKU.WHXB202309020","url":null,"abstract":"<div><div>Artificial photosynthesis is an appealing approach for generating hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) from H<sub>2</sub>O and O<sub>2</sub> with solar energy as the sole energy input. However, the current catalyst systems commonly face challenges such as the limited optical absorption, poor electron-hole pair separation efficiency, and restricted surface reactivity, which hinders the overall photoactivity. Here, we immobilize cubic-phase ultrathin In<sub>4</sub>SnS<sub>8</sub> nanosheets (<em>E</em><sub>g</sub> = 2.16 eV) with thickness of 5–10 nm on the surface of few-layer Ti<sub>3</sub>C<sub>2</sub> to develop a sandwich-like hierarchical structure of Ti<sub>3</sub>C<sub>2</sub>/In<sub>4</sub>SnS<sub>8</sub> nanohybrid <em>via in situ</em> hydrothermal strategy. The enlarged interfacial area and close contact between Ti<sub>3</sub>C<sub>2</sub> and In<sub>4</sub>SnS<sub>8</sub> benefit for carrier transportation among nanohybrids. Characterization through X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) corroborates the successful construction of Ti<sub>3</sub>C<sub>2</sub>/In<sub>4</sub>SnS<sub>8</sub> nanostructures. Band structures investigation including valence band maximum and Mott-Schottky plots reveals the formation of Schottky junction in this 2D/2D heterostructure, that favors for ultrafast charge carrier separation and transportation from In<sub>4</sub>SnS<sub>8</sub> to Ti<sub>3</sub>C<sub>2</sub> and preventing the electrons backflow from Ti<sub>3</sub>C<sub>2</sub> to In<sub>4</sub>SnS<sub>8</sub>. Photoluminescene analysis and photo/electrochemical measurements prove that the combination of Ti<sub>3</sub>C<sub>2</sub> and In<sub>4</sub>SnS<sub>8</sub> accelerates the transportation of photoexcited electron-hole pairs and efficiently suppresses charge carrier recombination. Unsurprisingly, 7 wt% Ti<sub>3</sub>C<sub>2</sub>/In<sub>4</sub>SnS<sub>8</sub> catalysts exhibit the highest visible-light-driven photoreactivity with H<sub>2</sub>O<sub>2</sub> production rates of 1.998 μmol∙L<sup>−1</sup>∙min<sup>‒1</sup> that is 2.2 times larger than that of single In<sub>4</sub>SnS<sub>8</sub>. Additionally, Ti<sub>3</sub>C<sub>2</sub>/In<sub>4</sub>SnS<sub>8</sub> demonstrates a multifunctional capability in Cr(VI) reduction with the greatest reaction rates of 19.8 × 10<sup>−3</sup> min<sup>‒1</sup> that is almost 4-fold larger than that of individual semiconductor. Moreover, the nanohybrids exhibit excellent photostability after 5 cycles testing in both reaction systems. The morphology, crystal structure and composition for Ti<sub>3</sub>C<sub>2</sub>/In<sub>4</sub>SnS<sub>8</sub> remain unaltered after photoreaction. A comprehensive analysis including trapping agents and atmosphere experiments as well as electron paramagnetic resonance demonstrates that the H<sub>2</sub>O<sub>2</sub> evolution pathway consists of two channels: a two-step successive 1e<sup>‒","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"40 10","pages":"Article 2309020"},"PeriodicalIF":10.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143155715","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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