Chinese Journal of Catalysis最新文献_第8页

Electrooxidation of PET alkaline hydrolysate to formate and glycolate enabled by the synergistic interaction of Ag and NiFe-LDH Ag和NiFe-LDH的协同作用使PET碱性水解液电氧化成甲酸盐和乙醇酸盐

IF 17.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2026-01-01 Epub Date: 2026-01-08 DOI: 10.1016/S1872-2067(25)64819-4

Yi Ma , Huan Ge , Yong Zhang , Ning Jian , Jialing Tang , Zongkun Hu , Jing Yu , Jordi Arbiol , Canhuang Li , Luming Li , Andreu Cabot , Junshan Li

Waste plastics present a significant threat to ecosystems and human health, necessitating efficient and cost-effective solutions for their conversion into high-value products. This study introduces a novel electrochemical reforming strategy to upgrade polyethylene terephthalate (PET) into valuable chemicals, primarily formic acid, while simultaneously generating hydrogen. A highly efficient electrocatalyst composed of nano-arrays of silver and NiFe layered double hydroxide (LDH) is synthesized via a hydrothermal and photo-precipitation process on a nickel foam substrate. This advanced catalyst achieves selective electrochemical conversion of ethylene glycol (EG) as PET hydrolysate to formate and glycolate with Faradaic efficiencies of 85% and 13% at 1.5 V vs. the reversible hydrogen electrode, with a stable and high current density. Density functional theory calculations reveal that the synergistic interaction between Ag and NiFe-LDH optimizes the adsorption and desorption of key intermediates on the catalytic sites, resulting in superior activity, selectivity, and stability for the electrochemical EG oxidation reaction. These findings highlight the potential of this catalyst for sustainable plastic waste valorization and renewable hydrogen production.

废塑料对生态系统和人类健康构成重大威胁，需要有效和具有成本效益的解决方案将其转化为高价值产品。本研究介绍了一种新的电化学重整策略，将聚对苯二甲酸乙二醇酯（PET）转化为有价值的化学品，主要是甲酸，同时产生氢气。采用水热法和光沉淀法在泡沫镍衬底上合成了一种由银和NiFe层状双氢氧化物（LDH）纳米阵列组成的高效电催化剂。与可逆氢电极相比，这种先进的催化剂在1.5 V电压下实现了将乙二醇（EG）作为PET水解物选择性转化为甲酸盐和乙醇酸盐的法拉第效率分别为85%和13%，具有稳定的高电流密度。密度泛函理论计算表明，Ag和NiFe-LDH之间的协同作用优化了催化位点上关键中间体的吸附和解吸，从而使电化学EG氧化反应具有更高的活性、选择性和稳定性。这些发现突出了这种催化剂在可持续塑料废物增值和可再生氢生产方面的潜力。

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引用次数: 0

Synergistic coupling of H2O2 production and furoic acid synthesis over B-TiO2@COF S-scheme bifunctional photocatalyst B-TiO2@COF s型双功能光催化剂上H2O2生成与呋喃酸合成的协同偶联

IF 17.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2026-01-01 Epub Date: 2026-01-08 DOI: 10.1016/S1872-2067(25)64870-4

Yandong Xu, Zihui Jing, Wenhao Su, Jiale Xu, Mingliang Wang

The synergistic coupling of photocatalytic hydrogen peroxide (H₂O₂) production and green organic synthesis not only optimizes utilization of photogenerated electron-hole pairs but also circumvents kinetically sluggish water oxidation reaction. In this study, an efficient composite photocatalyst was developed through in-situ growth of irregular TpPa-Cl blocks on the surface of boron-doped TiO₂, which boasts a large specific surface area. Boron doping enhances light absorption range and inhibits recombination of charge carriers. Additionally, deep integration of porous TiO₂ with TpPa-Cl improves the contact between the reactants and the photocatalyst, extends the carrier lifetime, and provides more active sites. In the absence of a co-catalyst, the yield of H₂O₂ reached 2082.6 μmol g⁻¹ h⁻¹, with a furfuryl alcohol conversion rate of 94%. In-situ XPS and density functional theory calculations confirmed S-scheme charge transfer mechanism, which enhances carrier separation and transfer efficiency while retaining photogenerated electrons and holes with strong redox properties. Quenching experiments, electron paramagnetic resonance, and in-situ diffuse reflectance infrared Fourier transformed spectroscopy demonstrated that H₂O₂ was primarily generated via a 2-electron oxygen reduction reaction with ·O₂⁻ and OOH* as intermediates. Furthermore, furfuryl alcohol was oxidized to the radical ·C₅H₅O₂ by h⁺ and subsequently converted to furfural or furoic acid through reactions with h⁺ or ·OH. This work presents a novel strategy for designing efficient composite photocatalysts for H₂O₂ production and green organic synthesis.

光催化过氧化氢（H2O2）生产与绿色有机合成的协同耦合不仅优化了光生电子-空穴对的利用，而且规避了动力学缓慢的水氧化反应。本研究通过在具有较大比表面积的硼掺杂TiO2表面原位生长不规则的TpPa-Cl块体，开发了一种高效的复合光催化剂。硼的掺杂提高了材料的光吸收范围，抑制了载流子的复合。此外，多孔TiO2与TpPa-Cl的深度集成改善了反应物与光催化剂之间的接触，延长了载体寿命，并提供了更多的活性位点。在无助催化剂的情况下，H2O2的产率达到2082.6 μmol g−1 h−1，糠醇的转化率为94%。原位XPS和密度泛函理论计算证实了S-scheme电荷转移机制，该机制增强了载流子分离和转移效率，同时保留了具有强氧化还原性质的光生电子和空穴。猝灭实验、电子顺磁共振和原位漫反射红外傅里叶变换光谱表明，H2O2主要是通过以·O2−和OOH*为中间体的2电子氧还原反应生成的。糠醇被h+氧化为自由基·C5H5O2，再与h+或·OH反应生成糠醛或糠酸。本研究提出了一种设计高效复合光催化剂用于H2O2生产和绿色有机合成的新策略。

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引用次数: 0

Fabrication of S-scheme heterojunction between covalent organic frameworks and Ni-ZIF-8 and its photocatalytic hydrogen production performance 共价有机骨架与Ni-ZIF-8间s型异质结的制备及其光催化制氢性能

IF 17.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2026-01-01 Epub Date: 2026-01-08 DOI: 10.1016/S1872-2067(25)64826-1

Xuan Zhang , Lin Zhou , Teng Yan , Xiaohu Zhang, Hao Chen

Covalent organic frameworks (COFs) have garnered significant attention in photocatalysis owing to their exceptional light absorption capacities, tunable band structures, and high specific surface areas. However, the rapid recombination of photogenerated carriers in COFs remains a critical bottleneck limiting their practical application. In this study, a novel S-scheme heterojunction was constructed by integrating a Ni-doped zeolitic imidazolate framework-8 (Ni-ZIF-8) with Py-COF, effectively addressing this challenge. Through precisely controlled synthesis, the heterojunction achieves efficient and stable material combination, which not only significantly enhances photogenerated charge separation efficiency and markedly reduces recombination rates, but also demonstrates outstanding catalytic performance (162.77 mmol·h⁻¹·g⁻¹) and cycling stability in hydrogen evolution reaction. This study provides new insights into the design of efficient ZIF/COF-based heterojunction catalysts. This study provides an important theoretical foundation for the design of high-performance photocatalytic materials with broad application prospects.

共价有机框架（COFs）由于其独特的光吸收能力、可调的带结构和高比表面积而在光催化领域引起了广泛的关注。然而，光生载流子在COFs中的快速重组仍然是限制其实际应用的关键瓶颈。在这项研究中，通过将ni掺杂的沸石咪唑盐框架-8 （Ni-ZIF-8）与Py-COF集成，构建了一个新的S-scheme异质结，有效地解决了这一挑战。通过精确控制合成，异质结实现了高效稳定的材料组合，不仅显著提高了光生电荷分离效率，显著降低了复合速率，而且在析氢反应中表现出优异的催化性能（162.77 mmol·h−1·g−1）和循环稳定性。本研究为设计高效的ZIF/ cof基异质结催化剂提供了新的思路。本研究为设计具有广阔应用前景的高性能光催化材料提供了重要的理论基础。

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引用次数: 0

Engineering of enzymatic modules for mRNA manufacturing: Advances in catalytic regulation and process integration mRNA制造的酶模块工程：催化调节和过程集成的进展

IF 17.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2026-01-01 Epub Date: 2026-01-08 DOI: 10.1016/S1872-2067(25)64860-1

Shiyi Che , Zhengjun Li , Zhiguo Su , Zhikao Li , Aibing Yu , Minsu Liu , Songping Zhang

The clinical efficacy of mRNA-based therapeutics is critically dependent on the structural integrity of the mRNA molecule, which in turn is governed by the efficiency and robustness of its manufacturing process. Unlike conventional small-molecule synthesis, mRNA manufacturing relies on complex enzymatic cascades involving biomacromolecules with dynamic conformations as templates, intermediates, and catalysts. Key enzymatic modules, including plasmid linearization for DNA template preparation (Module 1), in vitro transcription (IVT) synthesis (Module 2), capping modification (Module 3) of mRNA, and different nucleases-aided removal of impurities (Module 4), are highly interdependent, each with specific catalytic enzymes and auxiliary cofactors. These modules present major engineering challenges of low efficiency and lack of modular compatibility across the multi-step enzymatic processes. Moreover, traditional approaches such as multienzyme immobilization or compartmentalization often fail to meet the demands of high-throughput, continuous and scalable manufacturing. This review systematically summarizes recent advances in the engineering of enzymatic modules for mRNA manufacturing, emphasizing challenges in catalytic regulation, module integration and process intensification. The potential strategies for improving reaction compatibility and enabling process integration and intensification are discussed, providing insights into future directions for engineering mRNA synthesis at scale.

基于mRNA的治疗方法的临床疗效严重依赖于mRNA分子的结构完整性，而mRNA分子的结构完整性又取决于其制造过程的效率和稳健性。与传统的小分子合成不同，mRNA的制造依赖于复杂的酶级联反应，包括具有动态构象的生物大分子作为模板、中间体和催化剂。关键的酶模块，包括DNA模板制备的质粒线性化（模块1），体外转录（IVT）合成（模块2），mRNA的capping修饰（模块3），以及不同的核酸酶辅助去除杂质（模块4），都是高度相互依赖的，每个模块都有特定的催化酶和辅助辅因子。这些模块在多步骤酶促过程中存在效率低和缺乏模块兼容性的主要工程挑战。此外，多酶固定化或区隔化等传统方法往往无法满足高通量、连续和可扩展制造的需求。本文系统总结了mRNA制造酶模块工程的最新进展，强调了催化调控、模块集成和过程强化方面的挑战。讨论了改善反应相容性和使过程集成和强化的潜在策略，为大规模工程mRNA合成的未来方向提供了见解。

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引用次数: 0

Advances in multinuclear metal-organic frameworks for electrocatalysis 电催化用多核金属有机骨架的研究进展

IF 17.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2026-01-01 Epub Date: 2026-01-08 DOI: 10.1016/S1872-2067(25)64859-5

Liyuan Xiao, Zhenlu Wang, Jingqi Guan

Metal-organic frameworks (MOFs) with mononuclear metal ion nodes have garnered significant attention in the electrocatalytic field owing to their high surface area and tunable structures, but their development is critically hindered by the limitation of active site availability. In contrast, multinuclear MOFs exhibit notable advantages by offering multi-metal active sites, constructing complex structures, enhancing structural and thermal stability, and coupling with in-depth studies on catalytic mechanisms, endowing them great application potential in complex multi-electron reactions. This work provides a comprehensive review on the precise construction, in-situ characterizations, reaction mechanisms, modulation strategies, and electrocatalytic applications of multinuclear MOFs, underlying their role in electrocatalytic processes with a focus on adsorption, active sites, and electron transfer. The effects of spin, polarization, orbital coupling, and pore confinement on catalytic performance are systematically elucidated. Furthermore, the unique tuning strategies of multinuclear MOFs are summarized to guide the precise construction, including adjusting the type and number of metal cores, optimizing electronic structures, and manipulating defects. Lastly, the future trends in the development of multinuclear MOFs for electrocatalysis are envisioned, laying a solid foundation for their practical applications.

具有单核金属离子节点的金属有机骨架（mof）由于其高表面积和可调结构在电催化领域引起了广泛的关注，但其发展受到活性位点可用性的限制。相比之下，多核mof在提供多金属活性位点、构建复杂结构、增强结构和热稳定性以及与催化机理的深入研究相结合等方面具有显著的优势，在复杂的多电子反应中具有很大的应用潜力。本文综述了多核mof的精确结构、原位表征、反应机理、调制策略和电催化应用，以及它们在电催化过程中的作用，重点是吸附、活性位点和电子转移。系统地阐述了自旋、极化、轨道耦合和孔约束对催化性能的影响。此外，总结了多核mof的独特调谐策略，包括调整金属芯的类型和数量、优化电子结构和操纵缺陷，以指导精确构建。最后，展望了用于电催化的多核mof的未来发展趋势，为其实际应用奠定了坚实的基础。

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引用次数: 0

Alkali cation effects in electrochemical carbon dioxide reduction 碱阳离子在电化学二氧化碳还原中的作用

IF 17.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2026-01-01 Epub Date: 2026-01-08 DOI: 10.1016/S1872-2067(25)64834-0

Jiaqi Xiang , Limiao Chen , Shanyong Chen , You-Nian Liu

In recent decades, the unabated consumption of fossil fuels has resulted in a sustained increase in carbon dioxide emissions, exacerbating environmental challenges typified by the greenhouse effect, which has underscored the urgent imperative to develop highly efficient carbon dioxide capture and utilization technologies. The electrocatalytic carbon dioxide reduction reaction (eCO₂RR) has emerged as a promising strategy for the conversion of CO₂ into high-value-added chemical commodities. Recent investigations have demonstrated that alkali cations played a pivotal role in eCO₂RR, encompassing enhancements in catalytic activity and modulations of product selectivity. Despite these advancements, how exactly the alkali cations affect the electrocatalytic reaction process and the key determinants of alkali cation effects remain subjects of ongoing debate. We analyzed current research on the effects of alkali cations, in which the concentration and type of alkali cations were generally correlated with eCO₂RR performance. However, the distribution of alkali cations at the electrode interface is often overlooked. In this study, we first conclude recent advancements in electric double layer theory and elucidate three distinct modes of alkali cation distribution at the electrode-electrolyte interface. Subsequently, we systematically summarize the specific mechanisms through which these cations operate in different electrolyte systems. Furthermore, we propose fundamental perspectives for future investigations into alkali cation effects, aiming to provide guiding principles for the rational design of next-generation advanced eCO₂RR electrolysis systems.

近几十年来，化石燃料的持续消耗导致二氧化碳排放量持续增加，加剧了以温室效应为代表的环境挑战，这凸显了开发高效二氧化碳捕获和利用技术的紧迫性。电催化二氧化碳还原反应（eCO2RR）已成为将二氧化碳转化为高附加值化学商品的一种有前途的策略。最近的研究表明，碱离子在eCO2RR中发挥了关键作用，包括催化活性的增强和产物选择性的调节。尽管取得了这些进展，碱阳离子究竟如何影响电催化反应过程以及碱阳离子效应的关键决定因素仍然是持续争论的主题。我们分析了目前关于碱阳离子影响的研究，碱阳离子的浓度和类型通常与eCO2RR性能相关。然而，碱阳离子在电极界面的分布往往被忽视。在这项研究中，我们首先总结了电双层理论的最新进展，并阐明了碱阳离子在电极-电解质界面上的三种不同的分布模式。随后，我们系统地总结了这些阳离子在不同电解质体系中作用的具体机制。此外，我们对碱阳离子效应的未来研究提出了基本观点，旨在为下一代先进的eCO2RR电解系统的合理设计提供指导原则。

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引用次数: 0

Photocatalyzed C–N coupling reactions of small molecules 光催化小分子C-N偶联反应

IF 17.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2026-01-01 Epub Date: 2026-01-08 DOI: 10.1016/S1872-2067(25)64838-8

Lin-Xing Zhang , Chang-Long Tan , Ming-Yu Qi , Zi-Rong Tang , Yi-Jun Xu

Catalytic coupling of abundant CO₂ or renewable CH₃OH with nitrogenous small molecules, such as N₂, NH₃, and NO₃⁻, has emerged as a promising strategy for synthesizing high-value organonitrogen compounds. However, conventional thermal catalysis for C–N bond formation often relies on external chemical reagents and energy-intensive conditions, raising concerns about process sustainability. Photocatalysis offers a sustainable alternative by utilizing sunlight to generate high-energy electron-hole pairs in semiconductors, which can activate inert chemical bonds (e.g., C=O and N≡N) for programmed coupling under ambient conditions. In this review, we dissect the fundamental activation mechanisms underlying photon-mediated C‒N coupling reactions, highlight key recent breakthroughs in the synthesis of urea, formamide, and amino acids, and analyze persistent challenges alongside emerging opportunities. This work aims to deepen the understanding of photocatalytic C–N coupling reactions and inspire research interest in sustainable nitrogen fixation and carbon utilization.

丰富的CO2或可再生的CH3OH与含氮小分子（如N2、NH3和NO3−）的催化偶联已成为合成高价值有机氮化合物的一种有前途的策略。然而，传统的C-N键形成的热催化通常依赖于外部化学试剂和能源密集型条件，这引起了对过程可持续性的担忧。光催化提供了一种可持续的替代方案，利用阳光在半导体中产生高能电子-空穴对，这可以激活惰性化学键（例如，C=O和N≡N），在环境条件下进行程序化耦合。在这篇综述中，我们剖析了光子介导的C-N偶联反应的基本激活机制，重点介绍了尿素、甲酰胺和氨基酸合成方面的最新突破，并分析了持续存在的挑战和新兴的机遇。这项工作旨在加深对光催化C-N偶联反应的理解，激发对可持续固氮和碳利用的研究兴趣。

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引用次数: 0

Improving the electrocatalytic CO2 to formate conversion on bismuth using polyaniline as an electron pump 以聚苯胺为电子泵，改进了铋上电催化CO2制甲酸的转化

IF 17.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2026-01-01 Epub Date: 2026-01-08 DOI: 10.1016/S1872-2067(25)64833-9

Juxia Xiong , Hao Ma , Yingjun Dong , Benjamin Liu , Xiangji Zhou , Linbo Li , Yuanmiao Sun , Xiaolong Zhang , Hui-Ming Cheng

Bi-based catalysts are known to promote the electrochemical reduction of CO₂ to formic acid (HCOOH) or formate (HCOO⁻). However, their implementation presents challenges: the first H⁺/e⁻ pair transfer to form the key *OCHO intermediate on a Bi surface is a slow, kinetically sluggish endergonic process, resulting in a large overpotential and narrow potential window for high HCOOH/HCOO⁻ selectivity. Altering the localized p-orbital electron states of Bi to change intermediate binding behaviors is difficult. We addressed this problem by using an in-situ polymerization method to obtain a polyaniline-Bi hybrid (PANI-Bi) with Bi surrounded by PANI chains. Combined experimental and computational studies indicate that the polyaniline acted as an “electron pump” that facilitated charge transfer from the PANI backbone to the Bi surface and changed the p-orbital electrons of the Bi active sites. This lowered the energy barrier for the adsorption of intermediates and facilitated *OCHO formation. Consequently, a significant increase in formate production was observed, achieving a single-pass carbon efficiency exceeding 48.7% at 800 mA cm⁻². This organic functionalization strategy, aimed at modifying the electronic structure of heterogeneous catalysts, offers a promising approach for achieving highly selective electroreduction of CO₂ at a high current density.

已知铋基催化剂可以促进CO2电化学还原为甲酸（HCOOH）或甲酸（HCOO−）。然而，它们的实现面临着挑战：在Bi表面上形成键*OCHO中间体的第一次H+/e−对转移是一个缓慢的，动力学缓慢的自吸过程，导致高HCOOH/HCOO−选择性的过电位大，电位窗口窄。改变Bi的定域p轨道电子态来改变中间结合行为是很困难的。为了解决这一问题，我们采用原位聚合的方法得到了聚苯胺-铋杂化物（PANI-Bi）， Bi被PANI链包围。实验和计算相结合的研究表明，聚苯胺作为一个“电子泵”，促进电荷从聚苯胺骨架转移到Bi表面，改变了Bi活性位点的p轨道电子。这降低了中间体吸附的能垒，促进了*OCHO的形成。因此，甲酸产量显著增加，在800 mA cm−2下，单次碳效率超过48.7%。这种有机功能化策略旨在改变非均相催化剂的电子结构，为实现高电流密度下CO2的高选择性电还原提供了一种有前途的方法。

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引用次数: 0

Dual-site confinement strategy tuning Fe-N-C electronic structure to enhance oxygen reduction performance in PEM fuel cells 双位约束策略调整Fe-N-C电子结构以提高PEM燃料电池的氧还原性能

IF 17.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2026-01-01 Epub Date: 2026-01-08 DOI: 10.1016/S1872-2067(25)64804-2

Wenbo Shi , Kai Zhu , Xiaogang Fu , Chenhong Liu , Yang Yuan , Jialiang Pan , Qing Zhang , Zhengyu Bai

Single atomic iron-nitrogen-carbon (Fe-N-C) have emerged as promising catalysts for the oxygen reduction reaction (ORR), however, the insufficient activity and stability hindered their application in proton exchange membrane fuel cells (PEMFCs). Simultaneously regulating the coordination environments and local carbon structures of atomic Fe-N sites is essential to boost Fe-N-C's ORR performance. In this study, a dual-site confinement strategy is proposed to precisely incorporate Mn single atoms at adjacent Fe sites to form active and stable FeMn-N catalytic structure within a graphitic carbon matrix, which is achieved via heat treatment of MnFe₂O₄ nanoparticles embedded ZIF-8. Experimental and theoretical calculations demonstrate that the incorporation of Mn atoms could effectively modulate the electronic structure of Fe atoms, enhance Fe–N bond stability and reduce Fe site dissolution. Moreover, in-situ Raman and in-situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy spectra suggest that Mn doping could suppress Fenton reactions by optimizing the ORR pathway through facilitating *OH intermediate desorption and circumventing *OOH intermediate formation. The synthesized FeMn-N-C exhibits better catalytic activity than commercial Pt/C catalysts (E_1/2 of 0.885 vs. 0.855 V) and maintains stable cycling operation over 20000 cycles with a small E_1/2 gap of 95 mV. When applied in PEMFCs, FeMn-N-C achieves a high peak power density of 899.9 mW cm⁻² and retains 66.4% of its initial performance after 20000 square-wave cycles, which is superior to Fe-N-C catalyst. This study provides an innovative design strategy for developing high-performance, long-lasting ORR catalysts for PEMFCs.

单原子铁-氮-碳（Fe-N-C）已成为氧还原反应（ORR）的催化剂，但其活性和稳定性不足阻碍了其在质子交换膜燃料电池（pemfc）中的应用。同时调节Fe-N原子位的配位环境和局部碳结构对提高Fe-N- c的ORR性能至关重要。在本研究中，提出了一种双位点约束策略，通过热处理嵌入ZIF-8的MnFe2O4纳米颗粒，将Mn单原子精确地结合在相邻的Fe位点上，在石墨碳基体内形成活性稳定的FeMn-N催化结构。实验和理论计算表明，Mn原子的掺入可以有效地调节Fe原子的电子结构，增强Fe - n键的稳定性，减少Fe位点的溶解。此外，原位拉曼光谱和原位衰减全反射表面增强红外吸收光谱表明，Mn掺杂可以通过促进*OH中间体解吸和规避*OOH中间体形成来优化ORR途径，从而抑制Fenton反应。合成的FeMn-N-C催化剂的催化活性优于商用Pt/C催化剂（E1/2为0.885 vs. 0.855 V），在20000次循环中保持稳定的循环运行，e2 /2间隙很小，为95 mV。当FeMn-N-C应用于pemfc时，经过20000次方波循环，FeMn-N-C的峰值功率密度达到899.9 mW cm - 2，保持了66.4%的初始性能，优于Fe-N-C催化剂。该研究为开发高性能、长效的pemfc ORR催化剂提供了一种创新的设计策略。

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引用次数: 0

S-scheme heterojunctions of metal-doped ZnIn2S4/TpPa-1: Regulating H adsorption/desorption and internal electric field for boosted dual-functional photocatalysis 金属掺杂ZnIn2S4/TpPa-1的s型异质结：调节H吸附/解吸和增强双功能光催化的内部电场

IF 17.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2026-01-01 Epub Date: 2026-01-08 DOI: 10.1016/S1872-2067(25)64879-0

Shaodan Wang , Heng Yang , Lijun Xue , Jianjun Zhang , Shuxin Ouyang , Lili Wen

Cooperative coupling of photocatalytic hydrogen generation with oxidative organic synthesis is promising in simultaneously producing sustainable energy and value-added chemicals. However, the photocatalytic activity is constrained by restricted redox potentials and insufficient photocarrier separation and transfer. Herein, we construct S-scheme heterojunctions based on metal-doped ZnIn₂S₄ and covalent organic frameworks, denoted as M-ZIS/TpPa-1 (M = Ni or Mo). Theoretical calculations demonstrated that Mo-ZIS possess optimum H adsorption Gibbs free energies, deeper downshift of sulfur p-band center and higher integrated crystal orbital Hamilton population (ICOHP) value than Ni-ZIS and ZIS to optimize H adsorption/desorption dynamics. Besides, metal-doping reasonably enhanced the interfacial charge transfer in heterostructures, identifying the enlarged internal electric field (IEF) in Mo-ZIS/TpPa-1 than Ni-ZIS/TpPa-1 and ZIS/TpPa-1. Moreover, experimental explorations of photoelectrochemical measurements, femtosecond transient absorption spectroscopy, in-situ irradiated X-ray photoelectron spectroscopy and electron paramagnetic resonance verified the facilitated photocarrier separation and migration in metal-doped S-scheme heterojunctions. Ultimately, Mo_0.01-ZIS/TpPa-1 exhibited visible-light driven H₂ evolution rate of 1648 μmol g⁻¹ h⁻¹ and N-benzylidenebenzylamine formation rate of 1812 μmol g⁻¹ h⁻¹, better than Ni_0.048-ZIS/TpPa-1, and superior to parent ZIS/TpPa-1. This work might provide insights into the modulation of H adsorption/desorption behavior and IEF within S-scheme heterostructures via rational metal-doping strategy for efficient dual-functional photocatalysis.

光催化制氢与氧化有机合成的协同耦合在同时生产可持续能源和增值化学品方面具有广阔的前景。然而，光催化活性受到氧化还原电位受限和光载流子分离和转移不足的限制。在这里，我们构建了基于金属掺杂ZnIn2S4和共价有机框架的s方案异质结，记为M- zis /TpPa-1 （M = Ni或Mo）。理论计算表明，与Ni-ZIS和ZIS相比，Mo-ZIS具有最佳的H吸附吉布斯自由能、更深的硫p带中心下移和更高的集成晶体轨道汉密尔顿居群（ICOHP）值，从而优化H吸附/解吸动力学。此外，金属掺杂合理地增强了异质结构中的界面电荷转移，发现Mo-ZIS/TpPa-1的内部电场（IEF）比Ni-ZIS/TpPa-1和ZIS/TpPa-1的内部电场（IEF）更大。此外，光电化学测量、飞秒瞬态吸收光谱、原位辐照x射线光电子能谱和电子顺磁共振的实验探索证实了在金属掺杂的S-scheme异质结中促进光载流子的分离和迁移。最终，Mo0.01-ZIS/TpPa-1的可见光驱动H2进化速率为1648 μmol g−1 h−1，n -苄基苯胺生成速率为1812 μmol g−1 h−1，优于Ni0.048-ZIS/TpPa-1，优于亲本ZIS/TpPa-1。这项工作可能为通过合理的金属掺杂策略调节S-scheme异质结构中的H吸附/解吸行为和IEF提供新的见解，以实现高效的双功能光催化。

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