Journal of Catalysis最新文献_第5页

Synergistic regulation of charge dynamics and reaction pathways for selective photocatalytic NO oxidation to nitrate via oxygen vacancies and plasmonic Ag nanoparticles 通过氧空位和等离子体银纳米颗粒选择性光催化NO氧化成硝酸盐的电荷动力学和反应途径的协同调节

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-12-19 DOI: 10.1016/j.jcat.2025.116650

Dengyu Jiao , Peng Chen , Xing’an Dong , Jiazhen Liao , Wenjie He , Wendong Zhang

Selective photocatalytic oxidation of NO to nitrate (NO₃^–), rather than toxic NO₂, remains highly challenging due to uncontrollable reaction intermediates and extremely low charge migration efficiency. Herein, we design a photocatalyst (BiSbO₄/AgCl-Ag-70) that integrates a BiSbO₄/AgCl heterojunction with spatially correlated Ag nanoparticles (NPs) and oxygen vacancies (OVs) to synergistically regulated charge dynamics and reaction pathways. The formation of a heterojunction establishes a built-in electric field, which facilitates directional electron transfer. Meanwhile, Ag NPs and abundant OVs induce localized electron redistribution, promoting the generation of reactive oxygen species (ROS), and enhancing the selectivity toward nitrate. The BiSbO₄/AgCl-Ag-70 photocatalyst immobilized on ceramic foam achieved 90.0 % NO removal efficiency with excellent stability, maintaining 79.0 % removal after 720 min, while generating only 22 ppb (4.2 %) of toxic NO₂. Furthermore, the BiSbO₄/AgCl-Ag-70 catalyst demonstrated a high nitrate selectivity of 89.2 %. Mechanistic studies combining in situ DRIFTS and DFT calculations reveal that the introduction of OVs activates O₂/H₂O molecules, thereby promoting a reactive oxygen species-dominated pathway for the conversion of NO to NO₃^–, rather than the route involving the formation of the toxic intermediate NO₂. This work provides a strategy for the selective removal of NO by designing a material with rapid interface charge transfer and abundant surface active sites, thereby achieving precise regulation of the photocatalytic oxidation pathways.

由于不可控的反应中间体和极低的电荷迁移效率，将NO选择性光催化氧化为硝酸盐（NO3 -），而不是有毒的NO2，仍然是极具挑战性的。在此，我们设计了一种光催化剂（BiSbO4/AgCl-Ag-70），该催化剂将BiSbO4/AgCl异质结与空间相关的银纳米颗粒（NPs）和氧空位（OVs）结合起来，协同调节电荷动力学和反应途径。异质结的形成建立了一个内置的电场，这有利于定向电子转移。同时，Ag NPs和丰富的OVs诱导了局部电子再分配，促进了活性氧（ROS）的产生，增强了对硝酸盐的选择性。在陶瓷泡沫上固定化的BiSbO4/AgCl-Ag-70光催化剂的NO去除率为90.0 %，稳定性优异，在720 min后仍能保持79.0 %的去除率，而产生的有毒NO2仅为22 ppb（4.2 %）。此外，BiSbO4/AgCl-Ag-70催化剂的硝酸选择性高达89.2% %。结合原位DRIFTS和DFT计算的机制研究表明，OVs的引入激活了O2/H2O分子，从而促进了以活性氧为主的NO转化为NO3 -的途径，而不是涉及形成有毒中间体NO2的途径。本研究通过设计一种具有快速界面电荷转移和丰富表面活性位点的材料，从而实现光催化氧化途径的精确调控，为选择性去除NO提供了一种策略。

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引用次数: 0

Photo-generated hole mediated dynamic acid-base regulation in g-C3N4/Cr-MF/Cr2O3 composite for enhanced glucose photo-thermal conversion g-C3N4/Cr-MF/Cr2O3复合材料中光生空穴介导的动态酸碱调节增强葡萄糖光热转化

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-12-19 DOI: 10.1016/j.jcat.2025.116647

Min Li, Juanjuan Geng, Bing Feng, Tianyu Luan, Xumei Tao, Liang Huang

The selective conversion of glucose to 5-hydroxymethylfurfural (HMF) is crucial for sustainable biorefineries. The g-C₃N₄/Cr-MF/Cr₂O₃ composite was engineered by integrating photocatalytic and thermocatalytic functions, which synergistically balanced the Brønsted-to-Lewis acid ratio and enhanced charge carrier dynamics. Under 500 W Xe lamp irradiation and mild heat (150 °C, N₂), thermal energy served as the primary driving force, while photoexcitation selectively enhanced the catalysis by dual mechanisms. The catalyst established a spatiotemporal match between Lewis-acid-dominated glucose isomerization and Brønsted-acid-dominated dehydration at the bifunctional interface. Photo-generated holes potentiated Brønsted acidity via hole-proton synergy. This electronic and protonic-level modulation of the reaction pathway optimized the process, achieving exceptional glucose conversion (98.4 %) and HMF yield (52.8 %). This work established a generalizable framework for energy-coupled catalytic systems where light selectively accelerated specific steps within thermal reaction networks.

葡萄糖选择性转化为5-羟甲基糠醛（HMF）对可持续生物炼制至关重要。g-C3N4/Cr-MF/Cr2O3复合材料通过整合光催化和热催化功能，协同平衡Brønsted-to-Lewis酸比，增强载流子动力学。在500 W氙灯照射下（150℃，N2），热能为主要驱动力，光激发通过双机制选择性地增强了催化作用。该催化剂在双功能界面上建立了lewis酸主导的葡萄糖异构化和br ønsted酸主导的脱水的时空匹配。光产生的空穴通过空穴-质子协同作用增强了Brønsted的酸性。这种电子和质子水平的反应途径调节优化了该过程，实现了优异的葡萄糖转化率（98.4%）和HMF收率（52.8%）。这项工作为能量耦合催化系统建立了一个可推广的框架，其中光选择性地加速热反应网络中的特定步骤。

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引用次数: 0

Mechanism of Fe modulating NO/H2 reduction selectivity in Pd/Al2O3 catalyst for passive SCR Fe调节Pd/Al2O3催化剂中NO/H2还原选择性的机理

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-12-19 DOI: 10.1016/j.jcat.2025.116652

Peng Cheng , Meiqing Shen , Wei Li , Xinhua Li , Liwei Jia , Gurong Shen

Passive selective catalytic reduction (SCR) for hydrogen engine NO_x aftertreatment requires efficient NO-to-NH₃ conversion over three-way catalysts (TWC). However, conventional TWC formulations aim to maximize NO conversion to N₂, hence it is necessary to modify catalyst formulation and tailor the NO reduction selectivity towards NH₃. In this study, we examine the effect of surface coverage on NO reduction selectivity by comparing PdFe/Al₂O₃ and Pd/Al₂O₃. Through kinetic analysis combined with characterizations, we demonstrate that Fe enhances surface H* coverage by providing additional H₂ adsorption, and these H* species participate in NO reduction through spillover effect. Meanwhile Fe reduces the NO* coverage through reducing the electron density of Pd. Collectively, these changes regulate the relative surface coverage of NO* and H* (

θ_{NO} / θ_{H}

) during the reaction, leading to significant changes in reaction kinetics, inhibiting N₂O generation while improving NH₃ selectivity. This provides important insights for optimizing passive SCR catalysts.

氢发动机NOx后处理的被动选择性催化还原技术（SCR）要求通过三元催化剂（TWC）实现NO-to-NH3的高效转化。然而，传统的TWC配方旨在最大限度地将NO转化为N2，因此有必要修改催化剂配方，将NO还原选择性调整为NH3。在这项研究中，我们通过比较PdFe/Al2O3和Pd/Al2O3来研究表面覆盖对NO还原选择性的影响。通过动力学分析结合表征，我们证明了铁通过提供额外的H2吸附来提高表面H*的覆盖率，这些H*通过溢出效应参与NO的还原。同时Fe通过降低Pd的电子密度降低NO*的覆盖率。总的来说，这些变化调节了反应过程中NO*和H*的相对表面覆盖率（θNO/θH），导致反应动力学发生显著变化，抑制了N2O的生成，同时提高了NH3的选择性。这为优化无源SCR催化剂提供了重要的见解。

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引用次数: 0

Revisiting the activity of Ru-hcp(001) and Ru-fcc(111) for alkaline HER: A DFT study 重新考察Ru-hcp（001）和Ru-fcc（111）对碱性HER的活性：DFT研究

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-12-19 DOI: 10.1016/j.jcat.2025.116641

Lea Gašparič, Anton Kokalj

We present a comprehensive density-functional-theory (DFT) study of the water dissociation reaction on Ru-hcp(001) and Ru-fcc(111). The motivation stems from experiments showing that supported fcc-structured Ru nanoparticles outperform hcp-structured ones as catalysts for the hydrogen evolution reaction (HER) in alkaline media, as well as from prior combined experimental and computational work (Zheng et al., 2016) attributing this difference to intrinsic activity of the two facets derived from DFT calculations. By systematically varying slab thickness, supercell size, and water models, and by rigorously evaluating vibrational contributions to the Gibbs energy, we demonstrate that reaction Gibbs energies strongly depend on model details, whereas activation Gibbs energies are less sensitive. Importantly, when vibrational contributions are treated rigorously, water dissociation is predicted to exhibit slightly lower activation Gibbs energy on Ru-hcp(001), suggesting that it should be somewhat more active than Ru-fcc(111). This finding contrasts with the earlier aforementioned study, whose reported data reveal that Ru-fcc(111) is more active due to favorable vibrational contributions. This discrepancy stems primarily from the incomplete treatment of vibrational contributions in the earlier work and from the omission of corrections for low-frequency modes. Our results highlight the need to consider additional factors – such as support effects and the relative abundance and intrinsic activity of different facets present on Ru nanoparticles – to explain the experimentally observed superior alkaline HER activity of fcc-structured Ru nanoparticles. They further underscore the critical role of accurately evaluating vibrational Gibbs energy contributions in computational heterogeneous catalysis.

我们对Ru-hcp（001）和Ru-fcc（111）上的水解离反应进行了全面的密度泛函理论（DFT）研究。实验表明，负载的fcc结构的Ru纳米颗粒在碱性介质中作为析氢反应（HER）的催化剂的性能优于hcp结构的纳米颗粒，以及之前的实验和计算工作（Zheng et al., 2016）将这种差异归因于从DFT计算中得出的两个方面的内在活性。通过系统地改变板坯厚度、超级单体大小和水模型，并严格评估振动对吉布斯能的贡献，我们证明了反应吉布斯能强烈依赖于模型细节，而激活吉布斯能则不太敏感。重要的是，当振动贡献被严格处理时，预计水解离在Ru-hcp上的活化能略低（001），这表明它应该比Ru-fcc（111）更活跃。这一发现与前面提到的研究形成了对比，后者报道的数据显示，由于有利的振动贡献，Ru-fcc（111）更活跃。这种差异主要源于早期工作中对振动贡献的不完整处理以及对低频模态的修正的遗漏。我们的研究结果强调了需要考虑其他因素——例如支撑效应和Ru纳米颗粒上不同方面的相对丰度和内在活性——来解释实验观察到的fcc结构Ru纳米颗粒的优越碱性HER活性。他们进一步强调了在计算多相催化中准确评估振动吉布斯能贡献的关键作用。

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引用次数: 0

Rational design of Ni-Mo2N nitrogen carriers for high-efficiency chemical looping ammonia synthesis 高效化学环氨合成Ni-Mo2N氮载体的合理设计

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-12-19 DOI: 10.1016/j.jcat.2025.116651

Feiyue Guan , Tuo Guo , Guangmin Ren , Mengxuan Zhang , Man Wu , Qingjie Guo

Chemical looping ammonia synthesis (CLAS), an emerging green ammonia production technology, demonstrates significant potential in distributed ammonia synthesis. While early transition metal-based nitrogen carriers show promise in CLAS, their practical deployment has been hindered by inherent limitations in lattice nitrogen conversion and unsatisfactory NH₃ selectivity. Herein, we design a highly efficient Ni-Mo₂N composite nitrogen carrier synthesized via a one-step pyrolysis strategy. The optimized 25 % Ni-Mo₂N (molar ratio) system reaches an excellent lattice nitrogen conversion rate of 76 %. Ni-Mo₂N had an outstanding initial ammonia production rate of 9,050 μmol·g⁻¹·h⁻¹, whereas Mo₂N had an initial ammonia production rate of 3040 μmol·g⁻¹·h⁻¹. Crucially, the incorporation of Ni effectively suppresses the formation of Mo₂C during the pyrolysis process, ensuring the structural stability of the catalyst over 10 consecutive cycles and demonstrating 4.5-fold improvement compared to pristine Mo₂N. Theoretical calculations systematically unravel the CLAS reaction pathways occurring on Ni-Mo₂N surfaces and also reveal the synergistic interaction between Ni clusters and Mo₂N. This work establishes a foundational framework for developing next-generation high-efficiency CLAS systems.

化学环氨合成（CLAS）是一种新兴的绿色合成氨技术，在分布式合成氨方面具有巨大的潜力。虽然早期过渡金属基氮载体在CLAS中显示出前景，但它们的实际部署受到晶格氮转化的固有限制和不理想的NH3选择性的阻碍。为此，我们设计了一种高效的Ni-Mo2N复合氮载体，通过一步热解策略合成。优化后的25% Ni-Mo2N（摩尔比）体系的晶格氮转化率达到76%。Ni-Mo2N的初始产氨速率为9050 μmol·g−1·h−1，Mo2N的初始产氨速率为3040 μmol·g−1·h−1。关键是，Ni的加入有效地抑制了热解过程中Mo2C的形成，确保了催化剂在连续10个循环中的结构稳定性，与原始Mo2N相比，性能提高了4.5倍。理论计算系统地揭示了Ni-Mo2N表面发生的CLAS反应途径，并揭示了Ni簇与Mo2N之间的协同相互作用。该工作为开发下一代高效CLAS系统奠定了基础框架。

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引用次数: 0

First-principles design of YGaTe3 for bidirectional catalysis and shuttle suppression in lithium–sulfur batteries 用于锂硫电池双向催化和抑制穿梭的YGaTe3第一性原理设计

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-12-18 DOI: 10.1016/j.jcat.2025.116638

Qingyi Feng , Caizheng Wang , Bo Li , Sizhao Huang , Sean Li , Zhen Wang , Xia Xiang , Yangfang Li , Qiuquan Guo , Peipei Jia , Jun Yang

Lithium-sulfur (Li-S) batteries suffer from sluggish redox kinetics and polysulfide shuttle, which hinder their practical applications. Herein, first-principles calculations are employed to design and evaluate YGaTe₃ as a high-performance sulfur host. The Y-side surface exhibits nearly metallic conductivity (band gap = 0.0186 eV), providing efficient electron transport channels. Gibbs free energy profiles reveal uniformly low energy barriers (<0.20 eV) for the stepwise S₈ → Li₂S conversion on the Y-side, whereas the Ga-side exhibits a 0.45 eV barrier in the Li₂S₂ → Li₂S step. Furthermore, the continuous and thermodynamically favorable energy profiles during the charging process ensure the feasibility of LiPS oxidation and the capability of bidirectional catalysis. The NEB results demonstrate that the lower energy barrier on the Y-side (0.43 eV) compared to the Ga-side (0.72 eV) facilitates easier Li₂S activation and faster decomposition kinetics. The Bader charge analysis and −pCOHP results indicate the enhanced charge transfer and robust Te-Li bonding on the Y-side, while the p-band center calculations show stable and favorable electronic coupling for polysulfide adsorption. This combination of high conductivity, bidirectional catalysis, and shuttle suppression highlights YGaTe₃ as a promising candidate for stable and efficient Li-S batteries.

锂硫（li -硫）电池存在氧化还原动力学迟缓和多硫化物穿梭等问题，阻碍了其实际应用。本文采用第一性原理计算来设计和评估YGaTe3作为高性能硫宿主。y侧表面表现出接近金属的导电性（带隙= 0.0186 eV），提供了有效的电子传递通道。吉布斯自由能谱显示，在y侧S8→Li2S阶跃转化过程中，均匀的低能垒（<0.20 eV），而在Li2S2→Li2S阶跃转化过程中，ga侧的势垒为0.45 eV。此外，充电过程中连续且热力学上有利的能量分布保证了LiPS氧化的可行性和双向催化的能力。NEB结果表明，与ga侧（0.72 eV）相比，y侧（0.43 eV）的能垒较低，有利于Li2S更容易活化和更快的分解动力学。Bader电荷分析和- pCOHP结果表明，y侧的电荷转移和稳固的Te-Li键增强，而p带中心计算表明，多硫化物吸附稳定且有利的电子耦合。这种高导电性、双向催化和穿梭抑制的结合突出了YGaTe3作为稳定高效锂电池的有前途的候选者。

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引用次数: 0

Ir-catalyzed transfer hydrogenation and N-alkylation of N-heteroarenes with carboxylic acids ir催化n -杂芳烃与羧酸的转移加氢和n -烷基化反应

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-12-16 DOI: 10.1016/j.jcat.2025.116643

Jiaxin Liang, Yifei Wei, Yani Ge, Yilin Zhou, Jianhua Liao, Lu Ouyang, Renshi Luo

Given the importance of the N-heterocyclics and carboxylic acids, methods for editing these skeletons would be specifically valuable in drug discovery. In this work, we report a tandem Ir-catalyzed transfer hydrogenation and N-alkylation of N-heteroarenes with carboxylic acids as alkylated sources, which efficiently produces a series of N-alkylated tetrahydroquinolines and heterocycles in moderate to excellent yields (up to 96%) under air conditions. A wide range of carboxylic acids, including complex drug molecules and natural products, can be served as alkylated sources and incorporated into N-heteroarenes to afford a variety of useful structure motifs (66 examples). The successful gram-scale transformation, as well as diversification of natural molecules and drugs further highlight the practicality and robustness of this strategy, holding broad potential for the synthesis of bioactive N-alkylated heterocyclics from renewable feedstock.

考虑到n -杂环和羧酸的重要性，编辑这些骨架的方法在药物发现中将特别有价值。在这项工作中，我们报道了以羧酸为烷基化源的n -杂芳烃的串联ir催化转移加氢和n -烷基化，在空气条件下以中等到优异的收率（高达96%）高效地生产了一系列n -烷基化的四氢喹啉和杂环。广泛的羧酸，包括复杂的药物分子和天然产物，可以作为烷基化来源，并结合到n -杂芳烃中，以提供各种有用的结构基元（66个例子）。克级转化的成功，以及天然分子和药物的多样化，进一步凸显了这一策略的实用性和稳健性，为从可再生原料合成生物活性n -烷基化杂环化合物提供了广阔的潜力。

引用次数: 0

A robust Zr/Hf catalytic system for efficient and highly enantioselective α-hydroxylation of β-keto carbonyls and amides: mechanistic and DFT studies 一个强大的Zr/Hf催化体系，用于β-酮羰基和酰胺的高效和高对映选择性α-羟基化：机理和DFT研究

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-12-16 DOI: 10.1016/j.jcat.2025.116642

Cunfei Ma, Kun Tang, Jingnan Zhao, Yakun Wang, Yufeng Wu, Guofeng Zhao, Huinan Sun, Qilei Liu, Qingwei Meng

An efficient zirconium/hafnium catalytic system with low loading has been developed for the enantioselective α-hydroxylation of a series of substrates, including five-membered cyclic β-indanone esters, β-keto amides, and challenging 1-indanone-derived β-keto esters, delivering the products in high yields (up to 99%) with excellent enantioselectivities (up to 99% ee). The system also exhibits strong tolerance to variations in temperature and solvent, which ensures high efficiency and a broad substrate scope (42 examples). Its synthetic utility was demonstrated through gram-scale reactions and subsequent derivatization of product 2a. Mechanistic studies and DFT calculations revealed that C–H···π interactions between the substrate and the newly developed Salan ligand, along with π–π stacking with cumene hydroperoxide (CHP), are key to enantiocontrol.

本文开发了一种低负荷的锆铪催化体系，用于一系列底物的对映选择性α-羟基化，包括五元环β-吲哚酮酯、β-酮酰胺和1-吲哚酮衍生的β-酮酯，其产物收率高（高达99%），对映选择性高（高达99% ee）。该系统还对温度和溶剂的变化具有很强的耐受性，从而确保了高效率和广泛的基材范围（42个示例）。通过克级反应和随后的产物2a衍生化，证明了它的合成效用。机制研究和DFT计算表明，底物与新开发的Salan配体之间的C-H···π相互作用以及与过氧化氢异丙烯（CHP）的π -π堆积是对映体控制的关键。

引用次数: 0

Intrinsic partial oxidation of methane to formaldehyde on RhO2(1 1 0): disentangling oxygen depletion from electronic promotion 甲烷在RhO2上的本征部分氧化生成甲醛（11 10）：从电子促进中解缠氧耗尽

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-12-16 DOI: 10.1016/j.jcat.2025.116644

Dohyeon Kim, Minkyu Kim

The selective partial oxidation of methane to formaldehyde remains a fundamental challenge due to the strong tendency of CH₄-derived intermediates toward deep oxidation. Here, we combine density functional theory calculations and microkinetic simulations under ultra-high vacuum conditions to investigate the intrinsic reactivity of RhO₂ (1 1 0) toward CH₂O formation and to disentangle the roles of surface oxygen depletion from vacancy-induced electronic promotion. Simulated temperature-programmed reaction spectroscopy (TPRS) reveals a distinct coverage-dependent selectivity shift: CO₂ dominates at low CH₄ coverage, CH₂O emerges at intermediate coverage, and CH₄ recombinative desorption becomes significant at high coverage. CH₂O formation is maximized under moderately oxygen-deficient conditions, where the suppression of downstream oxidation enables thermal desorption of CH₂O_br intermediates. Electronic structure analyses and core-level shift calculations demonstrate that oxygen vacancies on RhO₂ (1 1 0) are structurally and electronically decoupled from the catalytically active Rh_cus sites, exerting negligible influence on C–H activation barriers or CH₂O formation kinetics. These findings reveal that CH₂O selectivity is governed predominantly by the thermodynamic and kinetic consequences of oxygen depletion rather than by electronic activation of the active site, highlighting the importance of decoupling structural and electronic effects when interpreting spectroscopic signatures of oxygen vacancies.

甲烷选择性部分氧化制甲醛仍然是一个根本性的挑战，因为甲烷衍生的中间体有强烈的深度氧化倾向。本文将密度泛函理论计算和超高真空条件下的微动力学模拟相结合，研究了RhO2（11 10）对CH2O形成的内在反应性，并揭示了空位诱导的电子促进对表面氧消耗的影响。模拟温度程序反应光谱（TPRS）揭示了明显的覆盖度依赖的选择性转移：低CH4覆盖度下CO2占主导地位，中等覆盖度下CH2O出现，高覆盖度下CH4重组解吸变得显著。在适度缺氧的条件下，CH2O的形成最大化，抑制下游氧化使CH2Obr中间体的热解吸成为可能。电子结构分析和核能级位移计算表明，RhO2（11 10）上的氧空位在结构和电子上与催化活性Rhcus位点解耦，对C-H活化障碍或CH2O形成动力学的影响可以忽略不计。这些发现表明，CH2O的选择性主要受氧消耗的热力学和动力学后果的影响，而不是由活性位点的电子激活决定的，这突出了在解释氧空位的光谱特征时解耦结构和电子效应的重要性。

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引用次数: 0

Interlayer stacking modulation of flexible covalent organic frameworks for broad-spectrum-driven H2O2 production in seawater 柔性共价有机框架层间堆叠调制用于海水中广谱驱动的H2O2生成

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-12-15 DOI: 10.1016/j.jcat.2025.116639

Yiping Chen , Xiangjing Xie , Xiayi Hu , Bei Long , Guo-Jun Deng , Ting Song

Compared with rigid covalent organic frameworks (COFs), flexible COFs exhibit adaptive structural dynamics that help mitigate collapse risks in harsh environments. However, their conformational flexibility often leads to bonding misorientation during synthesis, and precise interlayer stacking regulation remains challenging. Herein, we develop an aldehyde-mediated exchange strategy to construct three flexible COFs with tailored stacking modes: AA stacking (Sq-Ben-COF) mediated by benzaldehyde, AB stacking via 2-thiophenecarboxaldehyde, and unspecified stacking. Using only visible light and without sacrificial agents in natural seawater, Sq-Ben-COF achieved a record H₂O₂ production rate, surpassing AB-stacked and unspecified counterparts. Notably, Sq-Ben-COF also demonstrates photocatalytic H₂O₂ production activity under near-infrared light irradiation. Remarkably, all three COFs exhibited approximately 2-fold higher activity in seawater than in freshwater systems. Mechanistic insights reveal that AA stacking facilitates directional photoexcited electron migration, while optimized interlayer stacking enhances proton transport and active-site accessibility. This work establishes aldehyde exchange as a dual-functional approach to engineer ordered flexible COFs and regulate stacking modes, advancing their applications in energy and catalysis.

与刚性共价有机框架（COFs）相比，柔性COFs具有自适应结构动力学，有助于减轻恶劣环境下的崩溃风险。然而，它们的构象灵活性往往导致合成过程中的键取向错误，并且精确的层间堆叠调节仍然是一个挑战。在此，我们开发了一种醛介导的交换策略，构建了三种具有定制堆叠模式的柔性COFs：苯甲醛介导的AA堆叠（Sq-Ben-COF）， 2-噻吩甲醛介导的AB堆叠和非指定堆叠。在天然海水中，仅使用可见光且不使用牺牲剂，Sq-Ben-COF实现了创纪录的H2O2产率，超过了ab堆叠和未指定的同类产品。值得注意的是，Sq-Ben-COF在近红外光照射下也表现出光催化生成H2O2的活性。值得注意的是，所有三种COFs在海水中的活性都比在淡水系统中的活性高约2倍。机理分析表明，AA堆叠促进了定向光激发电子迁移，而优化的层间堆叠增强了质子传输和活性位点的可及性。本研究建立了醛交换作为设计有序柔性COFs和调节堆叠模式的双功能方法，推进了它们在能源和催化方面的应用。

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引用次数: 0