物理化学学报最新文献

{"title":"Bimetallic AuCu Alloy Decorated Covalent Organic Frameworks for Efficient Photocatalytic Hydrogen Production","authors":"Wenxiu Yang ,&nbsp;Jinfeng Zhang ,&nbsp;Quanlong Xu ,&nbsp;Yun Yang ,&nbsp;Lijie Zhang","doi":"10.3866/PKU.WHXB202312014","DOIUrl":"10.3866/PKU.WHXB202312014","url":null,"abstract":"<div><div>Covalent organic frameworks (COFs) represent a kind of novel crystalline porous organic substances with extended <em>π</em>-conjugation framework and tunable structures, which display great promise in photocatalysis. However, unadorned COFs suffer from sluggish reaction kinetics, and a cocatalyst is essentially needed to reduce the activation barrier toward specific surface reaction and accelerate reaction kinetics. In this work, bimetallic alloys serving as co-catalysts were decorated on COFs to enhance the photocatalytic hydrogen evolution performance. By precisely-tuning the ratio of AuCu alloy, the resultant Au₁Cu₅/COF-TpPa displays the highest photocatalytic hydrogen generation rate (8.24 mmol∙g⁻¹∙h⁻¹), even surpassing the Pt modified COF-TpPa (6.51 mmol∙h⁻¹∙g⁻¹). According to the systematic characterizations and theoretical calculation, Au₁Cu₅/COF-TpPa exhibits the significantly enhanced charge carrier separation efficiency and reduced H* formation energy barrier, thus possessing high photocatalytic performance. This work affords a valuable approach to advancing COF-based photocatalysts by employing bimetallic alloy cocatalysts.</div><div><span><figure><span><img><ol><li><span><span>Download: <span>Download high-res image (117KB)</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 2312014"},"PeriodicalIF":10.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143100465","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}

{"title":"Fabricating Micro/Nanostructured Separators and Electrode Materials by Coaxial Electrospinning for Lithium-Ion Batteries: From Fundamentals to Applications","authors":"Qi Li ,&nbsp;Pingan Li ,&nbsp;Zetong Liu ,&nbsp;Jiahui Zhang ,&nbsp;Hao Zhang ,&nbsp;Weilai Yu ,&nbsp;Xianluo Hu","doi":"10.3866/PKU.WHXB202311030","DOIUrl":"10.3866/PKU.WHXB202311030","url":null,"abstract":"<div><div>Highly coveted for their exceptional energy density, extended cycle life, impressive rate capability, and thermal stability, lithium-ion batteries (LIBs) stand out as the optimal power sources for real-world applications, ranging from portable electronics to electric vehicles (EVs). In this context, coaxial electrospinning has emerged as a compelling technique for fabricating nanofiber materials endowed with properties ideally suited for LIBs. These properties include a high specific surface area, exceptional porosity, a substantial aspect ratio, and facile surface modification. This comprehensive review encapsulates the fundamental principles, practical applications, and recent strides in coaxial electrospinning, particularly in the preparation of crucial LIB components such as cathodes, anodes, and separators. The intricate relationships between the micro/nanostructures of coaxially electrospun fiber materials and their resultant battery performances are meticulously examined. Additionally, the review outlines future directions and underscores the challenges inherent in advancing the field of coaxial electrospinning for LIBs.</div><div><span><figure><span><img><ol><li><span><span>Download: <span>Download high-res image (146KB)</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 2311030"},"PeriodicalIF":10.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143099715","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}

{"title":"Synergistic Effect of Cu-Graphdiyne/Transition Bimetallic Tungstate Formed S-Scheme Heterojunction for Enhanced Photocatalytic Hydrogen Evolution","authors":"Zhengyu Zhou ,&nbsp;Huiqin Yao ,&nbsp;Youlin Wu ,&nbsp;Teng Li ,&nbsp;Noritatsu Tsubaki ,&nbsp;Zhiliang Jin","doi":"10.3866/PKU.WHXB202312010","DOIUrl":"10.3866/PKU.WHXB202312010","url":null,"abstract":"<div><div>Cu-Graphdiyne and CoNiWO₄ were synthesized by organic and hydrothermal methods, respectively. The establishment of an S-scheme heterojunction between Cu-Graphdiyne and CoNiWO₄ was achieved by interface engineering design. The efficient separation and transfer of photogenerated carriers are facilitated by the synergistic effect of the built-in electric field and band bending, while maintaining the strong redox capacity of the catalysts. The introduction of Cu-Graphdiyne effectively enhances the photo absorption capacity and conductivity of the composite catalyst, and significantly suppresses the recombination of photogenerated carriers. The unique two-dimensional planar network structure of Cu-Graphdiyne provides abundant active sites for photocatalytic processes, thereby facilitating the photocatalytic reaction. Density functional theory (DFT) calculations demonstrate that hot electrons generated by surface plasmon resonance effects of Cu will transfer to Graphdiyne to promote hydrogen evolution reaction. This study offers insights into potential applications of Cu-Graphdiyne and nickel-cobalt based catalysts in photocatalytic hydrogen evolution.</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 10","pages":"Article 2312010"},"PeriodicalIF":10.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143100466","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}

{"title":"Spontaneously Improved Adsorption of H2O and Its Intermediates on Electron-Deficient Mn(3+δ)+ for Efficient Photocatalytic H2O2 Production","authors":"Xinyu Yin ,&nbsp;Haiyang Shi ,&nbsp;Yu Wang ,&nbsp;Xuefei Wang ,&nbsp;Ping Wang ,&nbsp;Huogen Yu","doi":"10.3866/PKU.WHXB202312007","DOIUrl":"10.3866/PKU.WHXB202312007","url":null,"abstract":"<div><div>Transitional metal oxyhydroxides have been demonstrated to be the reliable cocatalysts for water oxidation reaction. However, their insufficient adsorption ability for H₂O and its intermediate products during water oxidation greatly restricts the improvement of water oxidation rate. In this study, a spontaneously improved adsorption of H₂O and its intermediates on the electron-deficient Mn^{(3+<em>δ</em>)+} of MnOOH cocatalyst can greatly promote the rapid water oxidation to realize the efficient photocatalytic H₂O₂ production in a pure water system. In this case, amorphous MnOOH is selectively deposited on the (110) facet of AuPd-modified single-crystal BiVO₄ photocatalyst <em>via</em> the directionally photoinduced oxidation approach to produce AuPd/BiVO₄/MnOOH photocatalyst. Photocatalytic experiments exhibit that the as-prepared AuPd/BiVO₄/MnOOH (0.5%) photocatalyst obtains the boosted H₂O₂-evolution rate of 214 μmol∙L⁻¹ as well as exhibits an outstanding stability and reproducibility. Density functional theory calculations and X-ray photoelectron spectroscopy (XPS) characterization reveal that the free electrons of MnOOH can effectively transfer to BiVO₄ to induce the generation of electron-deficient Mn sites (Mn^{(3+<em>δ</em>)+}), which spontaneously promotes the adsorption of H₂O and its intermediates for enhancing 4-electron water oxidation reaction, resulting in an efficient H₂O₂ production. The present work about the strong interaction between cocatalyst and bulk catalyst provides a fresh idea for the rational design of highly efficient catalytic materials.</div><div><span><figure><span><img><ol><li><span><span>Download: <span>Download high-res image (103KB)</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 2312007"},"PeriodicalIF":10.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143155714","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}

{"title":"Integration of Plasmonic Effect and S-Scheme Heterojunction into Ag/Ag3PO4/C3N5 Photocatalyst for Boosted Photocatalytic Levofloxacin Degradation","authors":"Kexin Dong ,&nbsp;Chuqi Shen ,&nbsp;Ruyu Yan ,&nbsp;Yanping Liu ,&nbsp;Chunqiang Zhuang ,&nbsp;Shijie Li","doi":"10.3866/PKU.WHXB202310013","DOIUrl":"10.3866/PKU.WHXB202310013","url":null,"abstract":"<div><div>The escalating presence of pharmaceutical antibiotics in natural water poses an overwhelming threat to the sustainable development of society. Photocatalysis technology stands out as a promising and cutting-edge environmental purification alternative. C₃N₅, identified as a distinctive nonprecious nonmetal photocatalyst, holds potential for environmental protection. However, challenges persist originating from the sluggish photoreaction kinetics and severe photo-carrier reunion. Currently, the design of a special S-scheme photosystem proves to be a reliable strategy for obtaining outstanding photocatalysts. In this context, a plasmonic S-scheme photosystem involving Ag/Ag₃PO₄/C₃N₅ was developed through a feasible route. The compactly connected 0D/0D/2D Ag/Ag₃PO₄/C₃N₅ heterostructure, benefitting from the synergy between the plasmonic effect and the S-scheme junction, facilitates the efficient utilization of appreciably reinforced sunlight absorption, effective photo-carrier disassociation, and notable photoredox capacity. Consequently, this system generates •OH and \u0000\t\t\t\t<span><math><mrow><mo>⋅</mo><msubsup><mtext>O</mtext><mtext>2</mtext><mo>-</mo></msubsup></mrow></math></span> effectively. Ag/Ag₃PO₄/C₃N₅ demonstrates a superb photocatalytic levofloxacin eradication rate of 0.0362 min⁻¹, marking a substantial advancement of 24.8, 1.1, and 0.7 folds compared to C₃N₅, Ag₃PO₄, and Ag₃PO₄/C₃N₅, respectively. Impressively, Ag/Ag₃PO₄/C₃N₅ delivers remarkable anti-interference performance and reusability. This achievement signifies a significant step toward developing potent C₃N₅-involved photosystems for environmental purification.</div><div><span><figure><span><img><ol><li><span><span>Download: <span>Download high-res image (106KB)</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 2310013"},"PeriodicalIF":10.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143099755","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}

{"title":"Electrocarboxylation of Benzylic Phosphates and Phosphinates with Carbon Dioxide","authors":"Xiaofei Liu,&nbsp;He Wang,&nbsp;Li Tao,&nbsp;Weimin Ren,&nbsp;Xiaobing Lu,&nbsp;Wenzhen Zhang","doi":"10.3866/PKU.WHXB202307008","DOIUrl":"10.3866/PKU.WHXB202307008","url":null,"abstract":"&lt;div&gt;&lt;div&gt;Carbon dioxide (CO&lt;sub&gt;2&lt;/sub&gt;) serves as a non-toxic, abundant, cheap, and renewable C1 feedstock in synthetic chemistry. The synthesis of high value-added fine chemicals, such as organic carboxylic acids, using CO&lt;sub&gt;2&lt;/sub&gt;, is always a focal point of research. Due to the thermodynamic stability and kinetic inertness of carbon dioxide, traditional carboxylation reactions utilizing CO&lt;sub&gt;2&lt;/sub&gt; often require harsh reaction conditions. However, organic electrochemical synthesis, which employs electrons as clean reagents to drive the reaction and avoids additional chemical oxidants or reductants, has emerged as a safer, more economical, highly selective, sustainable, and environmentally friendly method for preparing fine chemicals. Electrocarboxylation, which leverages organic electrochemical synthesis to catalytically transform CO&lt;sub&gt;2&lt;/sub&gt;, provides a milder and more efficient route for CO&lt;sub&gt;2&lt;/sub&gt; utilization. Among these approaches, electrocarboxylation of organic halides or pseudohalides containing C―X bonds with CO&lt;sub&gt;2&lt;/sub&gt; has been extensively investigated as a means to access value-added carboxylic acids. Phosphates, known for their good leaving group properties, find extensive applications in organic synthesis. Under reductive conditions, the radical anion generated by benzyl phosphate easily dissociates into a benzyl radical and a phosphate anion. Hence, it can serve as an attractive substrate for participating in electrocarboxylation reactions. In this study, we report the highly efficient electrocarboxylation of benzylic phosphate and phosphinate derivatives using CO&lt;sub&gt;2&lt;/sub&gt; as the carboxyl source. The constant current reaction took place in an undivided cell, employing glassy carbon as the cathode, and magnesium as the sacrificial anode, in a mixed solvent of DMF and THF. Additionally, this mild electrolysis can be carried out under nonsacrificial anode conditions, using cheap carbon felt electrode as both the nonsacrificial anode and cathode and &lt;em&gt;N&lt;/em&gt;,&lt;em&gt;N&lt;/em&gt;-diisopropylethylamine as an external reductant, therefore provided operationally simple and highly efficient synthetic method toward aryl acetic acids in moderate to good yield. The broad substrate scope, simple operation, facile scalability, and highly efficient transformation of phosphates into high value-added aryl acetic acids under mild conditions demonstrate the potential applicability of this reaction. To gain insight into the possible reaction mechanism, several control experiments were conducted. Isotope-labeling [&lt;span&gt;&lt;span&gt;&lt;sup&gt;13&lt;/sup&gt;&lt;/span&gt;&lt;/span&gt;]CO&lt;sub&gt;2&lt;/sub&gt; experiment, cyclic voltammetry experiments, radical trapping reactions, and deuterium-labeling experiment indicated that cathodically generated benzylic radical and benzylic anion were key intermediates. Moreover, the single electron reduction of CO&lt;sub&gt;2&lt;/sub&gt; to \u0000\t\t\t\t&lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;msubsup&gt;&lt;mrow&gt;&lt;mtext&gt;CO&lt;/mtext&gt;&lt;/mrow&gt;&lt;mn&gt;2&lt;/mn&gt;&lt;mrow&gt;&lt;mo&gt;⋅&lt;/mo&gt;&lt;mo&gt;-&lt;/mo&gt;&lt;/mrow&gt;&lt;/msu","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"40 9","pages":"Article 2307008"},"PeriodicalIF":10.8,"publicationDate":"2024-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87021822","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}

{"title":"Regulating HER and OER Performances of 2D Materials by the External Physical Fields","authors":"Chunling Qin ,&nbsp;Shuang Chen ,&nbsp;Hassanien Gomaa ,&nbsp;Mohamed A. Shenashen ,&nbsp;Sherif A. El-Safty ,&nbsp;Qian Liu ,&nbsp;Cuihua An ,&nbsp;Xijun Liu ,&nbsp;Qibo Deng ,&nbsp;Ning Hu","doi":"10.3866/PKU.WHXB202307059","DOIUrl":"10.3866/PKU.WHXB202307059","url":null,"abstract":"&lt;div&gt;&lt;div&gt;Hydrogen fuel has long been considered a promising and practical alternative to conventional fossil fuels for shaping the future of our energy landscape. The electrocatalytic water-splitting technique, a sustainable and eco-friendly technology, provides a viable solution for efficiently and abundantly producing high-purity hydrogen on a large scale. However, practical applications of this technology require continuous improvement in the reaction kinetics for the hydrogen evolution reaction (HER) at the anode and the oxygen evolution reaction (OER) at the cathode. Additionally, ongoing optimization of the catalyst's catalytic activity and structural stability is crucial for the practical implementation of this technology. The selection of suitable catalysts is of paramount importance in water splitting. As a result, two-dimensional (2D) nanomaterials have become a focal point in water electrolysis due to their unique physicochemical properties and abundant active sites. The atomic thinness of 2D materials makes their electronic structure easily adjustable, allowing for the precise control of electrocatalytic performance through morphological modifications, defect engineering, phase transitions, cocatalyst deposition, and element doping. However, the complex system structure design and the potentially mutual interference of various chemical components could hinder further improvements in hydrogen evolution performance. Fortunately, the distinctive physicochemical characteristics of 2D materials can synergize with external physical fields, leading to enhanced electrocatalytic performance through distinct effects. For example, magnetic fields, electric fields, and light fields can induce thermal effects, effectively reducing charge transfer resistance and bubble coverage on the catalyst surface. Strain can regulate the &lt;em&gt;d&lt;/em&gt;-band center, thus controlling adsorption energy. Moreover, the superposition of multiple physical fields and the multiple effects of a single physical field offer enormous potential for enhancing electrocatalytic performance. It is evident that the regulation of electrocatalytic performance through physical fields holds significant untapped potential. Consequently, the roles and mechanisms of external physical field assistance in HER and OER have garnered increasing attention. External fields such as electric fields, magnetic fields, strain, light, temperature, and ultrasound can be applied to synthesis and electrocatalysis. This paper first provides a summary of research on the synthesis of physical field-assisted electrolytic water catalysts. It then classifies studies on field-assisted HER and OER based on different mechanisms. Finally, it outlines the key challenges and prospects in this rapidly evolving research field.&lt;/div&gt;&lt;div&gt;&lt;span&gt;&lt;figure&gt;&lt;span&gt;&lt;img&gt;&lt;ol&gt;&lt;li&gt;&lt;span&gt;&lt;span&gt;Download: &lt;span&gt;Download high-res image (76KB)&lt;/span&gt;&lt;/span&gt;&lt;/span&gt;&lt;/li&gt;&lt;li&gt;&lt;span&gt;&lt;span&gt;Download: &lt;span&gt;Download full-size image&lt;/span&gt;&lt;/sp","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"40 9","pages":"Article 2307059"},"PeriodicalIF":10.8,"publicationDate":"2024-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"136372676","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}

{"title":"Influence of PC-based Electrolyte on High-Rate Performance in Li/CrOx Primary Battery","authors":"Rui Yang ,&nbsp;Hui Li ,&nbsp;Qingfei Meng ,&nbsp;Wenjie Li ,&nbsp;Jiliang Wu ,&nbsp;Yongjin Fang ,&nbsp;Chi Huang ,&nbsp;Yuliang Cao","doi":"10.3866/PKU.WHXB202308053","DOIUrl":"10.3866/PKU.WHXB202308053","url":null,"abstract":"&lt;div&gt;&lt;div&gt;The Li/CrO&lt;sub&gt;&lt;em&gt;x&lt;/em&gt;&lt;/sub&gt; battery has gained attention in the construction of smart cities, aerospace, and national defense and military applications due to its high energy density and excellent rate performance. Developing a Li/CrO&lt;sub&gt;&lt;em&gt;x&lt;/em&gt;&lt;/sub&gt; battery with high specific capacity, high energy density, excellent magnification performance, long storage life, and low cost is a primary goal. In this pursuit, the role of the electrolyte in battery performance for Li/CrO&lt;sub&gt;&lt;em&gt;x&lt;/em&gt;&lt;/sub&gt; primary batteries cannot be underestimated. However, current research on Li/CrO&lt;sub&gt;&lt;em&gt;x&lt;/em&gt;&lt;/sub&gt; primary batteries has primarily focused on electrode materials, with limited attention given to the electrolyte. Propylene carbonate (PC) solvent possesses a wide temperature range for melting and boiling points (−48.8 to 242 °C) and a high dielectric constant of 64.92. As a result, it is frequently used as a key component in electrolytes that operate under extreme temperatures and high rates. Nevertheless, its use in Li/CrO&lt;sub&gt;&lt;em&gt;x&lt;/em&gt;&lt;/sub&gt; batteries remains limited. Developing electrolyte systems based on PC with a wide temperature range and high dielectric constant is crucial for the advancement of high-power and environmentally robust lithium primary batteries. In this study, we investigated the discharge behavior of CrO&lt;sub&gt;&lt;em&gt;x&lt;/em&gt;&lt;/sub&gt; in PC-based electrolytes and identified suitable electrolyte systems for high-current discharge, specifically a 1 mol∙L&lt;sup&gt;−1&lt;/sup&gt; LiTFSI PC : DOL (1,3-dioxolane) = 1 : 2 ratio. We also demonstrated that the coordination number of solvent molecules in the solvation sheath layer around Li&lt;sup&gt;+&lt;/sup&gt; ions and the solvated structure involved in coordination significantly influence the rate performance of Li/CrO&lt;sub&gt;&lt;em&gt;x&lt;/em&gt;&lt;/sub&gt; battery systems in PC-based electrolytes. Reducing the coordination number of solvent molecules facilitates the desolvation behavior of solvated Li&lt;sup&gt;+&lt;/sup&gt;, thereby enhancing the desolvation process on the material surface. Furthermore, lowering the coordination number of solvent molecules promotes the involvement of anions in the solvated sheath structure. When the coordination number of solvent molecules falls below 3, it tends to form a solvated coordination structure involving anions with a higher lowest unoccupied molecular orbital (LUMO) level. This enables anions to participate in forming a solid electrolyte interface (SEI), resulting in a thinner and denser SEI film that significantly improves battery performance. Ultimately, modifying the coordination number for PC-based electrolytes is a practical and effective approach to enhance the rate performance of solvated sheath structures. The coordination number and the solvated sheath structure of Li&lt;sup&gt;+&lt;/sup&gt; in PC-based electrolytes have a profound impact on the high-current-discharge performance of the Li/CrO&lt;sub&gt;&lt;em&gt;x&lt;/em&gt;&lt;/sub&gt; battery system. A lower coordination number and the participation of anions i","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"40 9","pages":"Article 2308053"},"PeriodicalIF":10.8,"publicationDate":"2024-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"136372437","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}

{"title":"Nickel-Vanadium Layered Double Hydroxides for Efficient and Scalable Electrooxidation of 5-Hydroxymethylfurfural Coupled with Hydrogen Generation","authors":"Meiran Li ,&nbsp;Yingjie Song ,&nbsp;Xin Wan ,&nbsp;Yang Li ,&nbsp;Yiqi Luo ,&nbsp;Yeheng He ,&nbsp;Bowen Xia ,&nbsp;Hua Zhou ,&nbsp;Mingfei Shao","doi":"10.3866/PKU.WHXB202306007","DOIUrl":"10.3866/PKU.WHXB202306007","url":null,"abstract":"<div><div>Electrocatalytic water splitting driven by renewable energy is a potential approach to obtain green hydrogen. However, the relatively high overpotential of anodic oxygen evolution reaction (OER) is one of the main obstacles hindering the widespread popularity of water electrocatalysis technology. To this end, electrochemical hydrogen-evolution coupled with the oxidation of biomass derived platforms, such as replacing OER with thermodynamically favorable 5-hydroxymethylfurfural (HMF) oxidation reaction (HMFOR), provides an efficient strategy to lower energy utilization and co-producing valuable organic oxygenates. For instance, 2,5-furandicarboxylic acid (FDCA) is emerging as an important and value-added industrial chemical obtained from HMFOR, which can be used as the monomer of various sustainable bioplastics (e.g., polyesters, polyamides). Great efforts have been devoted to this arena on electrocatalyst engineering for better activity and product selectivity. However, less work has focused on the process scalability of HMFOR to FDCA. Here, we report a simple hydrothermal method to fabricate an array-structured nickel-vanadium layered double hydroxides (NiV-LDH) growth on nickel foam matrix, demonstrating large-sized (6 cm × 10 cm) synthesis of self-supported electrode. The as-prepared material is active and efficient for HMFOR, achieving 100 mA∙cm⁻² of current density at 1.52 V <em>vs.</em> reversible hydrogen electrode (RHE) with 94.6% of Faradaic efficiency and 89.1% of yield to FDCA. Compared to traditional water splitting, replacing OER with HMFOR improves the counterpart hydrogen production rate by two-times. As proof-of-concept, we demonstrate the continuous and scalable HMFOR using a low-cost and membrane-free flow reactor system with electrode area of 49.5 cm². Under a constant current of 10 A, this system achieves high HMF single-pass conversion (94.8%), high FDCA concentration (~186.8 mmol∙L⁻¹), and high FDCA selectivity (98.5%) using 200 mmol∙L⁻¹ of HMF feedstock at a flow rate of 3.62 mL∙min⁻¹. Finally, gram-scale FDCA (119.5 g) can be obtained with hydrogen production using water electrolysis technology. This work highlights that catalyst design and system engineering should be coupled in the future rather than continuing in parallel directions.</div><div><span><figure><span><img><ol><li><span><span>Download: <span>Download high-res image (66KB)</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 9","pages":"Article 2306007"},"PeriodicalIF":10.8,"publicationDate":"2024-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74113838","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}

{"title":"Photothermal Synthesis of Glycerol Carbonate via Glycerol Carbonylation with CO2 over Au/Co3O4-ZnO Catalyst","authors":"Yajin Li ,&nbsp;Huimin Liu ,&nbsp;Lan Ma ,&nbsp;Jiaxiong Liu ,&nbsp;Dehua He","doi":"10.3866/PKU.WHXB202308005","DOIUrl":"10.3866/PKU.WHXB202308005","url":null,"abstract":"<div><div>Glycerol carbonylation with CO₂ to synthesize glycerol carbonate is a promising approach for CO₂ utilization. This reaction can be achieved through a thermally-driven catalytic pathway, but it is constrained by thermodynamic equilibrium. In the present study, we introduced solar energy into the reaction system to enable a photo-thermal synergistic catalytic reaction, breaking through the thermodynamic limitations. We developed a series of <em>x</em>Au/20Co₃O₄-ZnO catalysts, where Co₃O₄-ZnO, a composite of p-type semiconductor Co₃O₄ and n-type semi-conductor ZnO, exhibited a heterojunction structure, and Au nanoparticles loaded onto the surface of Co₃O₄-ZnO revealed the localized surface plasmon resonance (LSPR). We investigated the ability of <em>x</em>Au/Co₃O₄-ZnO to absorb visible light absorption, the efficiency of separating photo-generated hole-electron pairs, and the impact of Au on the photothermal synergistic catalytic performances of Au/Co₃O₄-ZnO catalysts. We also examined the effects of Au doping on the bulk and surface properties, including crystalline structures, morphologies, specific surface areas and pore structures, the binding energies of the elements, surface acid-base sites, and reduction behaviors of <em>x</em>Au/Co₃O₄-ZnO. Our findings revealed that the heterojunction structure of Au/20Co₃O₄-ZnO facilitated visible light absorption and hole-electron pair separation. The size of Au nano-particles (NPs) loaded on Co₃O₄-ZnO surface was approximately 50 nm. The loading of Au altered the electron density of Co and Zn, improved the reducibility of Co species, and enhanced the presence of oxygen vacancies on Co₃O₄-ZnO surface. The LSPR of Au NPs further enhanced the visible light absorption capacity of Au/20Co₃O₄-ZnO, and improved the separating of photo-generated hole-electron pairs, thus enhancing the photothermal catalytic performances. With the optimizing conditions (150 °C, 5 MPa, 6 h, and 225 W visible light irradiation), the 2%Au/20Co₃O₄-ZnO catalyst demonstrated excellent performances, yielding a glycerol carbonate yield of 6.5%. This study is expected to serve as a reference for the rational design of improved photothermal catalysts for glycerol carbonylation with CO₂ to produce glycerol carbonate in the future.</div><div><span><figure><span><img><ol><li><span><span>Download: <span>Download high-res image (89KB)</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 9","pages":"Article 2308005"},"PeriodicalIF":10.8,"publicationDate":"2024-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"136372706","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}