ChemSusChem最新文献_第9页

Nitroxyl Radical-Enhanced Proton-Coupled Electron Transfer for the Selective Oxidation of Biomass-Derived 5-Hydroxymethylfurfural. 硝基自由基增强质子耦合电子转移选择性氧化生物质衍生的5-羟甲基糠醛。

IF 6.6 2区化学

ChemSusChem Pub Date : 2025-09-26 DOI: 10.1002/cssc.202501492

Wenjing Wang, Ling Zhang, Taikang Jia, Bei Jiang, Mengya Xu, Ruofan Li, Chuanqi Zhang, Wenzhong Wang

{"title":"Nitroxyl Radical-Enhanced Proton-Coupled Electron Transfer for the Selective Oxidation of Biomass-Derived 5-Hydroxymethylfurfural.","authors":"Wenjing Wang, Ling Zhang, Taikang Jia, Bei Jiang, Mengya Xu, Ruofan Li, Chuanqi Zhang, Wenzhong Wang","doi":"10.1002/cssc.202501492","DOIUrl":"https://doi.org/10.1002/cssc.202501492","url":null,"abstract":"The selective oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), a key monomer for degradable plastics, is crucial for biomass valorization and addressing plastic pollution. However, its efficiency is limited by high energy barriers and slow kinetics due to the complex multi-electron and multi-proton transfer steps. Herein, a MIL-100(Fe)/TEMPO/nitric acid catalyst system is developed to facilitate electron transfer in HMF oxidation. The catalyst system achieves 100% conversion of 3 wt% HMF in 16 h at 353 K and atmospheric pressure, with a 94% yield of total acid product. The cyclic voltammetry and in situ electron paramagnetic resonance (EPR) reveal that nitric acid promotes TEMPO oxidation to TEMPO+, facilitating electron transfer and increasing the oxidation rate. The Griess method, ferrocene cation probe, and in situ EPR confirm nitric oxide (NO) formation, which acts as an electron shuttle between oxygen and MIL-100(Fe), accelerating the Fe(III)/Fe(II) redox cycle. Hydrogen/deuterium kinetic isotope effect analysis supports a proton-coupled electron transfer (PCET) mechanism. This study demonstrates that nitric acid significantly enhances PCET, enabling rapid oxidation of HMF to FDCA under mild conditions.","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202501492"},"PeriodicalIF":6.6,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145147063","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}

引用次数: 0

A Methodology for the Analysis of Water Oxidation Electrocatalysts in the Absence of Limiting Current that Avoids the Pitfalls of Existing Methods. 一种在没有限制电流的情况下分析水氧化电催化剂的方法，避免了现有方法的缺陷。

IF 6.6 2区化学

ChemSusChem Pub Date : 2025-09-26 DOI: 10.1002/cssc.202500778

Colton J Breyer, Diane K Smith, Jing Gu, Douglas B Grotjahn

{"title":"A Methodology for the Analysis of Water Oxidation Electrocatalysts in the Absence of Limiting Current that Avoids the Pitfalls of Existing Methods.","authors":"Colton J Breyer, Diane K Smith, Jing Gu, Douglas B Grotjahn","doi":"10.1002/cssc.202500778","DOIUrl":"https://doi.org/10.1002/cssc.202500778","url":null,"abstract":"Water oxidation is an important reaction studied as a way to generate electrons from water, to promote water splitting and the formation of green hydrogen. When using electrodes to drive homogeneous water oxidation catalysis, cyclic voltammograms are analyzed to provide catalytic rate constants. There are two main methods, foot-of-the-wave analysis (FOWA) and limiting current analysis. FOWA relies on approximations inherent to analyzing water oxidation catalysis, such as determining the formal potential of the catalytic intermediate, <math> <semantics> <mrow> <msub><msup><mi>E</mi> <mn>0</mn></msup> <mrow><mi>c</mi> <mi>a</mi> <mi>t</mi></mrow> </msub> </mrow> <annotation>$$ {{E}^{0}}_{cat} $$</annotation></semantics> </math> . Limiting current methods are the optimal way to analyze catalyst performance but rely on observable limiting current, which is virtually never seen in water oxidation. To avoid those issues, a method is proposed for analyzing nonideal cyclic voltammetry waveshapes in water oxidation: by analyzing rate data across a large range of potentials, an optimal potential, <math> <semantics> <mrow> <msub><mrow><mi>E</mi> <mo>'</mo></mrow> <mrow><mi>c</mi> <mi>a</mi> <mi>t</mi></mrow> </msub> </mrow> <annotation>$$ {{E}^{text{&amp;amp;amp;amp;amp;aposx;}}}_{cat}$$</annotation></semantics> </math> , can be obtained, where catalytic current, <math> <semantics> <mrow><msub><mi>i</mi> <mrow><mi>c</mi> <mi>a</mi> <mi>t</mi></mrow> </msub> </mrow> <annotation>$i_{c a t}$</annotation></semantics> </math> , is nearly independent of scan rate and has a linear dependency on buffer concentration. The method is applied to four homogeneous water oxidation catalysts with prior extensive electrochemical elucidation, all of which lack an ideal, purely kinetic waveshape in cyclic voltammetry. Application of the method avoids the biases of the other methods cited for the kinetic analyses of water oxidation catalysts.","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202500778"},"PeriodicalIF":6.6,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145147108","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}

引用次数: 0

Core and End-Capped Engineering as a Powerful Tool in the Search of Long-Term High-Performance Dye-Sensitized Solar Cells. 核心和端盖工程是寻找长期高性能染料敏化太阳能电池的有力工具。

IF 6.6 2区化学

ChemSusChem Pub Date : 2025-09-26 DOI: 10.1002/cssc.202501564

Matías J Alonso-Navarro, Santiago Franco, Fátima Suárez-Blas, Raquel Andreu, Jesús Orduna, M Mar Ramos, José L Segura

引用次数: 0

Modulation of Self-Assembly and Enhanced Photocatalytic H₂ Production by Porphyrin-Dipeptide Conjugates. 卟啉-二肽缀合物对自组装和增强光催化制氢的调节作用。

IF 6.6 2区化学

ChemSusChem Pub Date : 2025-09-25 DOI: 10.1002/cssc.202501251

Evitina Triantafyllou, Emmanouil Nikoloudakis, Sotiris Psilodimitrakopoulos, Dimitrios Kavalieros, Georgios Landrou, Emmanuel Stratakis, Georgios Charalambidis, Anna Mitraki, Athanassios G Coutsolelos

{"title":"Modulation of Self-Assembly and Enhanced Photocatalytic H2 Production by Porphyrin-Dipeptide Conjugates.","authors":"Evitina Triantafyllou, Emmanouil Nikoloudakis, Sotiris Psilodimitrakopoulos, Dimitrios Kavalieros, Georgios Landrou, Emmanuel Stratakis, Georgios Charalambidis, Anna Mitraki, Athanassios G Coutsolelos","doi":"10.1002/cssc.202501251","DOIUrl":"https://doi.org/10.1002/cssc.202501251","url":null,"abstract":"Herein, it is reported the visible-light-induced green hydrogen generation from self-assembled porphyrin-dipeptide hybrids. For the first time the self-assembly ability of a protected alanine-phenylalanine dipeptide is investigated via a simple protocol, which proved efficient in forming well-defined fibrillar architectures. These self-assembling properties are conveyed to peptide-porphyrin chromophores after their covalent conjugation. Interestingly, different architectures are observed depending on the solvent system, the solvent evaporation rate, the presence of metal in the porphyrin core, and the peripheral substitution of the porphyrin. Moving one step forward, it is explored the activity of the self-assembled nanostructures towards photocatalytic green H2 production from aqueous protons under visible-light irradiation. The distinct self-assembly behavior of the synthesized conjugates and their impact on photocatalytic hydrogen production is systematically explored in this study. Nonlinear second harmonic generation optical measurements are employed to define how the shape of the nanostructures is related to the H2 production efficiency. Notably, the tubular nanostructures presented the best catalytic performance, achieving a high H2 production activity of 32.7 mmol·g-1·h-1. Through detailed characterization and performance evaluation, it is aimed to uncover new insights into the design and optimization of peptide-porphyrin-based photocatalysts for sustainable energy applications.","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202501251"},"PeriodicalIF":6.6,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145135905","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}

引用次数: 0

Light-Switchable Pickering Emulsions Emulsified by Spiropyran-Based Ionic Liquid Surfactants and UiO-66-NH₂. 螺旋吡喃基离子液体表面活性剂和UiO-66-NH2乳化的可调光酸洗乳。

IF 6.6 2区化学

ChemSusChem Pub Date : 2025-09-25 DOI: 10.1002/cssc.202501618

Zhiyong Li, Linhui Niu, Liufang Zhao, Yunlei Shi, Huiyong Wang, Yang Zhao, Jianji Wang

{"title":"Light-Switchable Pickering Emulsions Emulsified by Spiropyran-Based Ionic Liquid Surfactants and UiO-66-NH2.","authors":"Zhiyong Li, Linhui Niu, Liufang Zhao, Yunlei Shi, Huiyong Wang, Yang Zhao, Jianji Wang","doi":"10.1002/cssc.202501618","DOIUrl":"https://doi.org/10.1002/cssc.202501618","url":null,"abstract":"The main goals of catalytic reactions are to minimize catalyst use, reduce activation energy, and shorten reaction time. Pickering emulsions offer an effective platform for achieving these goals. A key challenge is developing simple, efficient methods that enable fast reactions, easy product separation, catalyst recovery, and emulsifier reuse. Herein, a light-switchable oil-in-water (O/W) Pickering emulsion composed of a spiropyran-based ionic liquid surfactant, UiO-66-NH2, toluene, and water is presented. The system can reversibly transition between demulsification and emulsification under alternating visible and ultraviolet light. This feature enables the O/W Pickering emulsion to function as a precisely controlled interfacial catalysis reactor for synthesizing hydrophilic products via Click reaction. The catalytic platform is highly efficient, requiring minimal catalyst loading. It reduces activation energy from 33.6 to 8.5 kJ mol-1, a fourfold decrease, and improves conversion efficiency by more than 50%. Under visible light, the spiropyran structure in water shifts from a hydrophilic open-ring MC form to a hydrophobic closed-ring SP configuration. This structural change enhances the adsorption capacity of the spiropyran-based ionic liquid surfactant on UiO-66-NH2 and increases its partition coefficient between toluene and water. At the same time, the surfactant's surface activity decreases, which explains the light-responsive phase behavior of Pickering emulsions.","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202501618"},"PeriodicalIF":6.6,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145147055","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}

引用次数: 0

Bioinspired Construction of Proton-Coupled Electron Transfer Pathways in Covalent Organic Frameworks for Enhanced Photosynthesis of Hydrogen Peroxide. 以生物为灵感构建共价有机框架中质子耦合电子转移途径以增强过氧化氢的光合作用。

IF 6.6 2区化学

ChemSusChem Pub Date : 2025-09-25 DOI: 10.1002/cssc.202501760

Aodi Wang, Lingyu Xiang, Guoqing Wang, Xueling Song, Hangxun Xu, Lei Wang

{"title":"Bioinspired Construction of Proton-Coupled Electron Transfer Pathways in Covalent Organic Frameworks for Enhanced Photosynthesis of Hydrogen Peroxide.","authors":"Aodi Wang, Lingyu Xiang, Guoqing Wang, Xueling Song, Hangxun Xu, Lei Wang","doi":"10.1002/cssc.202501760","DOIUrl":"https://doi.org/10.1002/cssc.202501760","url":null,"abstract":"Covalent organic frameworks (COFs) have emerged as promising photocatalysts for the artificial photosynthesis of hydrogen peroxide (H2O2), yet their practical application is hindered by limited photocatalytic efficiency. Herein, a bioinspired strategy is reported to enhance the photocatalytic performance of COFs by introducing an ortho-positioned arrangement of enol (OH) and imine (N) groups. Through rational molecular engineering, a concerted proton-coupled electron transfer (PCET) pathway is established, which facilitates the efficient separation and transfer of photoexcited charge carriers, thereby dramatically enhancing H2O2 production from water and oxygen. The TbDO COF, featuring the PCET pathway, demonstrates superior performance, achieving a remarkable H2O2 production rate of 7265 μmol g-1 h-1 in a nonsacrificial system, surpassing COFs with similar structure but lacking this pathway. This study advances the design of COFs and opens new avenues for sustainable solar-to-chemical energy conversion.","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202501760"},"PeriodicalIF":6.6,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145135973","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}

引用次数: 0

Front Cover: Closed-Loop Recyclable Vitrimer Plastics from PET Waste: A Design for Circularity (ChemSusChem 18/2025) 封面：从PET废料中回收的闭环玻璃体塑料：循环设计（ChemSusChem 18/2025）

IF 6.6 2区化学

ChemSusChem Pub Date : 2025-09-23 DOI: 10.1002/cssc.70131

Mary K. Danielson, Catalin Gainaru, Zoriana Demchuk, Chuyi Pan, Jihye Choi, Hong-Hai Zhang, Jeffrey C. Foster, Tomonori Saito, Md Anisur Rahman

引用次数: 0

Oxidation of 5-Hydroxymethylfurfural over ZnIn₂S₄/Ti₃C₂T_x Photocatalyst Modulated by Sulfur Vacancy Defects and Schottky Heterojunctions. 硫空位缺陷和Schottky异质结调控ZnIn2S4/Ti3C2Tx光催化剂上5-羟甲基糠醛的氧化反应

IF 6.6 2区化学

ChemSusChem Pub Date : 2025-09-23 DOI: 10.1002/cssc.202501504

Xiaoping Wang, Bowen Yang, Haoye Wang, Haixin Guo, Richard Lee Smith, Yaqiong Su, Xinhua Qi

{"title":"Oxidation of 5-Hydroxymethylfurfural over ZnIn2S4/Ti3C2Tx Photocatalyst Modulated by Sulfur Vacancy Defects and Schottky Heterojunctions.","authors":"Xiaoping Wang, Bowen Yang, Haoye Wang, Haixin Guo, Richard Lee Smith, Yaqiong Su, Xinhua Qi","doi":"10.1002/cssc.202501504","DOIUrl":"https://doi.org/10.1002/cssc.202501504","url":null,"abstract":"Conversion of biomass into chemical products with solar energy is an important avenue for technological sustainability. Constructing efficient Schottky heterojunctions with vacancy defects can be a productive approach for achieving photooxidation of 5-hydroxymethylfurfural (HMF). Herein, sulfur vacancy (Vs) defect-enriched ZnIn2S4 is combined with Ti3C2Tx MXene (Vs-ZIS/MX) containing Schottky heterojunctions via self-assembly to form photocatalysts for efficient oxidation of HMF to 2,5-diformylfuran (DFF) under air-ambient conditions. HMF conversion of 87.3% with 72.9% DFF selectivity is obtained by the Vs-ZIS/MX heterojunction photocatalyst under visible light (420 nm < λ <780 nm, 2 h). Density functional theory calculations reveal that the Schottky heterojunction and regulated S vacancies enhance the electronic coupling and lower HMF adsorption energy, establishing a directional electron transfer channel from Vs-ZIS to MXene and an enhanced built-in electric field. Extended X-ray absorption fine structure spectroscopy shows that a stable metal (Zn)O bond coordination is formed between Vs-ZIS and MXene, and the enrichment of local electrons at S vacancy defects sites and metal-O coordination makes it possible to extract the delocalized electrons from ZIS to MXene. This work demonstrates a method to modulate the electron cloud density and enhance transport with a built-in electric field on photogenerated carriers for catalytic conversion of organic alcohols.","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202501504"},"PeriodicalIF":6.6,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145123874","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}

引用次数: 0

Cover Feature: How to Produce Green Hydrogen from Olivine and Seawater? By Ultrasound (ChemSusChem 18/2025) 封面专题：如何从橄榄石和海水中生产绿色氢？超声检测（ChemSusChem 18/2025）

IF 6.6 2区化学

ChemSusChem Pub Date : 2025-09-23 DOI: 10.1002/cssc.70134

Sergey I. Nikitenko, Tony Chave

引用次数: 0

Cover Feature: Exploring Acrylic Acid as an Oxirane Nucleophile: Direct Access to Poly(β-Hydroxy Acrylates) (ChemSusChem 18/2025) 封面专题：探索丙烯酸作为氧烷亲核试剂：直接获得聚（β-羟基丙烯酸酯）（ChemSusChem 18/2025）

IF 6.6 2区化学

ChemSusChem Pub Date : 2025-09-23 DOI: 10.1002/cssc.70133

Céline Montanari, Lukas Marcos Celada, Wenhao Zhang, Peter Olsén

引用次数: 0