Green Chemistry最新文献_第4页

Hydrogen bond interactions on a dual-core copper catalyst promote the activation of low-concentration CO2 and the generation of ethylene 双核铜催化剂上的氢键相互作用促进了低浓度CO2的活化和乙烯的生成

IF 9.2 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2026-01-22 Epub Date: 2026-01-28 DOI: 10.1039/d5gc06841j

Guodong Sun , Yingfei Ma , Yanan Cao , Kaiyang Zhao , Kewen Ao , Xinqi Wang , Mingtian Hao , Mengchen Sun , Wei Zhang

The electroreduction of low-concentration carbon dioxide to ethylene is highly attractive, as it enables the utilization of dilute CO₂ in flue gas while producing high-value-added chemicals. However, the inherent difficulty of activating CO₂ at low concentrations has limited both the catalytic activity and ethylene selectivity of existing copper-based electrocatalysts. In principle, precise regulation of the coordination microenvironment in copper-based complex catalysts could substantially lower the energy barriers associated with CO₂ activation and C–C coupling, thereby enhancing CO₂-to-C₂H₄ conversion; nevertheless, this strategy remains largely unexplored. Here, we perform theoretical calculations on CO₂-to-C₂H₄ conversion over binuclear copper coordination complexes, [Cu₂(OH)₂L₂]-X (L = 1,10-phenanthroline or 2,2′-bipyridine; X = external anion), featuring OH⁻ bridging ligands. We demonstrate that the oxygen atoms of the OH⁻ ligands surrounding the binuclear copper centers form hydrogen bonds with the hydrogen atom of the *COOH intermediate, significantly lowering the energy barrier for CO₂ activation. Moreover, the adjacent Cu⋯Cu sites effectively promote C–C coupling, facilitating ethylene formation. Electrochemical CO₂ reduction tests reveal that the [Cu₂(OH)₂L₂]-X complexes exhibit outstanding catalytic activity and C₂H₄ selectivity, achieving faradaic efficiencies of up to 62.5% and 58.8%, respectively. This work offers a new design paradigm for highly efficient copper-based complex catalysts for the electroreduction of CO₂ to multicarbon products.

将低浓度二氧化碳电还原为乙烯极具吸引力，因为它能够利用烟气中的稀释二氧化碳，同时生产高附加值化学品。然而，在低浓度下活化CO2的固有困难限制了现有铜基电催化剂的催化活性和乙烯选择性。原则上，精确调控铜基络合催化剂的配位微环境可以大幅降低CO2活化和C-C偶联相关的能垒，从而提高CO2-to- c2h4的转化；然而，这一策略在很大程度上仍未得到探索。在这里，我们对双核铜配位配合物[Cu2(OH)2L2]-X （L = 1,10-菲罗啉或2,2 ' -联吡啶；X =外阴离子）上二氧化碳到c2h4的转化进行了理论计算，该配合物具有OH -桥接配体。我们证明了围绕双核铜中心的OH -配体的氧原子与*COOH中间体的氢原子形成氢键，显著降低了CO2活化的能垒。此外，相邻的Cu⋯Cu位点有效地促进了C-C偶联，促进了乙烯的形成。电化学CO2还原实验表明，[Cu2(OH)2L2]-X配合物具有出色的催化活性和C2H4选择性，法拉第效率分别高达62.5%和58.8%。这项工作为高效铜基复合催化剂的设计提供了一个新的范例，用于电还原二氧化碳到多碳产品。

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引用次数: 0

Ethanol-assisted mechanochemical synthesis of MOF-199-derived CuOx/carbon composites with tunable copper species for photo-enhanced Fenton-like dye degradation 乙醇辅助机械化学合成mof -199衍生CuOx/碳复合材料及其可调铜种，用于光增强fenton类染料降解

IF 9.2 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2026-01-22 Epub Date: 2026-02-10 DOI: 10.1039/d5gc05389g

Khoa D. Tran , Hoan T. Phan , Khoa A. Nguyen , Khoa A. N. Van , Ha V. Le , Huy X. Le , Phuoc H. Ho , Ha P. K. Huynh , Khoa D. Nguyen

Metal–organic frameworks (MOFs) are attractive precursors for constructing porous metal–carbon composites, yet their conventional solvothermal synthesis relies heavily on toxic solvents and energy-intensive conditions. Herein, we develop an ethanol-assisted mechanochemical strategy for the rapid and solvent-minimal synthesis of MOF-199, followed by controlled pyrolysis to obtain MOF-199-derived CuO_x/carbon composites with tunable copper species. Electron microscopy reveals that copper-based nanoparticles are uniformly embedded and confined within the porous carbon matrix. X-ray diffraction and X-ray photoelectron spectroscopy confirm the coexistence of Cu, Cu₂O, and CuO in the as-prepared materials, revealing distinct bulk and surface copper speciation that depends on pyrolysis temperature. Among the obtained catalysts, the sample CuO_x/C-700, which was pyrolysed at 700 °C, shows a significant Cu₂O/CuO phase and demonstrates outstanding performance as a visible-light-enhanced Fenton-like catalyst for rhodamine B degradation in the presence of H₂O₂. It achieves 98.6% removal within 180 min at near-neutral pH, significantly outperforming the reaction in the dark. Radical scavenging experiments identify ˙OH as the dominant reactive species, while LC-HRMS analysis reveals progressive deethylation and ring-opening degradation pathways. Furthermore, the catalyst demonstrates good recyclability, is applicable to various dyes, and has low copper leaching, highlighting its structural robustness. This work establishes a green and scalable mechanochemical route to engineer MOF-derived Cu-based photo-Fenton-like catalysts, where controlled copper speciation and nanoscale confinement enhance the efficiency of wastewater remediation.

金属有机骨架（mof）是构建多孔金属碳复合材料的有吸引力的前驱体，但其传统的溶剂热合成严重依赖于有毒溶剂和能源密集型条件。在此，我们开发了一种乙醇辅助的机械化学策略，用于快速和溶剂最少的MOF-199合成，然后通过受控热解获得MOF-199衍生的CuOx/碳复合材料，其中铜种可调。电子显微镜显示，铜基纳米颗粒均匀地嵌入并限制在多孔碳基体中。x射线衍射和x射线光电子能谱证实了Cu、Cu2O和CuO在制备的材料中共存，揭示了不同的体铜和表面铜形态取决于热解温度。在所得到的催化剂中，在700℃下进行热解的CuOx/C-700样品显示出明显的Cu2O/CuO相，并且在H2O2存在下表现出优异的可见光增强fenton类催化剂降解罗丹明B的性能。在接近中性的pH值下，180分钟内达到98.6%的去除率，明显优于在黑暗条件下的反应。自由基清除实验表明˙OH是主要的活性物质，而LC-HRMS分析揭示了渐进式去甲基化和开环降解途径。此外，该催化剂具有良好的可回收性，适用于各种染料，铜浸出率低，突出了其结构稳健性。这项工作建立了一个绿色和可扩展的机械化学路线来设计mof衍生的cu基光fenton类催化剂，其中控制铜形态和纳米级限制提高了废水修复的效率。

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引用次数: 0

Accelerated HER kinetics via electron-deficient Ni and electron-enriched Se sites by dual Fe and Mn doping for highly efficient hydrogen production 通过双Fe和Mn掺杂，通过缺电子Ni和富电子Se位点加速HER动力学，实现高效产氢

IF 9.2 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2026-01-22 Epub Date: 2026-01-27 DOI: 10.1039/d5gc06340j

Guanglin Zhu , Lili Ren , Bo Gao , Cean Guo , Jianjia Mu , Fang Gu , Zhongbao Feng

The rational design of efficient and stable non-noble electrocatalysts for the hydrogen evolution reaction (HER) is vital but still challenging. Doping strategies have recently been explored for Ni-based selenides, but the synergistic modulation of dual-valence states, especially by coupling with low-valence Fe and high-valence Mn in Ni_0.85Se, has rarely been reported; additionally, their roles in promoting HER dynamics remain unclear. Herein, we demonstrate the facile synthesis of Fe and Mn dual-doped Ni_0.85Se (Fe/Mn-Ni_0.85Se) on Ni foam (NF) by electrodeposition, followed by selenization for the HER. Benefiting from the co-modulation of Fe and Mn, the electronic environment of Ni and Se in Fe/Mn-Ni_0.85Se is finely tuned, leading to accelerated charge transfer and high HER performance. The resulting Fe/Mn-Ni_0.85Se exhibits a small overpotential of 137.3 mV at an ampere level of 2 A cm⁻², with a remarkable stability of 100 h at 500 mA cm⁻². This can be closely related to the fact that dual doping with low-valence Fe and high-valence Mn in Ni_0.85Se can create electron-rich Se sites to accelerate water dissociation and electron-deficient Ni sites to promote proton recombination simultaneously, thereby synergistically lowering the energy barrier and boosting the overall HER activity. The present work offers a universal and guiding strategy to prepare high-performance electrocatalysts with dual doping of low-valence and high-valence metals for industrial-level hydrogen production.

合理设计高效、稳定的析氢非贵金属电催化剂至关重要，但仍具有挑战性。近年来，人们对镍基硒化物的掺杂策略进行了探索，但对Ni0.85Se中双价态的协同调制，特别是与低价Fe和高价Mn的耦合，很少有报道；此外，它们在促进HER动态中的作用仍不清楚。在此，我们展示了在Ni泡沫（NF）上电沉积Fe和Mn双掺杂Ni0.85Se (Fe/Mn-Ni0.85Se)，然后在HER上进行硒化。得益于Fe和Mn的共调制，Fe/Mn- ni0.85 Se中Ni和Se的电子环境得到了很好的调节，从而加速了电荷转移和提高了HER性能。所得Fe/Mn-Ni0.85Se在2 a cm−2的安培水平下表现出137.3 mV的小过电位，在500 mA cm−2下具有100小时的显著稳定性。这可能与Ni0.85Se中低价Fe和高价Mn的双重掺杂可以同时产生富电子Se位点加速水解离和缺电子Ni位点促进质子重组密切相关，从而协同降低能垒，提高整体HER活性。本研究为制备高效能的低价和高价金属双掺杂电催化剂提供了一种通用的指导策略。

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引用次数: 0

Pyramidal Ni nanoparticles with highly coordinated surfaces enabled by metal–support interaction regulation for efficient H2 production from NH3 具有高度配位表面的锥体镍纳米颗粒，通过金属支撑相互作用调节，使NH3高效产氢

IF 9.2 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2026-01-22 Epub Date: 2026-02-10 DOI: 10.1039/d5gc05524e

Zheng Li , Jun-Jun Yao , Jia-Ning Song , Jun-Kang Guo , Dong Zhang , Hui-Juan Wang , Ji-Zhou Yang , Shuang-Feng Yin

Catalytic ammonia decomposition represents a highly efficient and environmentally friendly route for hydrogen production. Ni-based catalysts, renowned for their cost-effectiveness, have emerged as promising alternatives to noble metal catalysts. However, the influence of Ni nanoparticle morphology on catalytic performance remains underexplored. In this study, we report the construction of pyramidal Ni nanoparticles supported on CeO₂–Al₂O₃ by tuning metal–support interactions. This innovative approach significantly enhances catalytic efficiency, achieving 75.62% NH₃ conversion at 500 °C under a weight hour space velocity of 30 000 mL g_(cat)⁻¹ h⁻¹, while maintaining excellent stability over 1000 h of continuous operation. Comprehensive characterization combined with DFT calculations reveals that pyramidal Ni nanoparticles exhibit a higher proportion of highly coordinated surface sites than their spherical counterparts. The d-band center was lowered by the combined geometric and electronic effects, which weakens the Ni–N bond and facilitates N–N recombination, thereby accelerating the reaction rate. This research highlights the critical role of active metal morphology in governing catalytic behavior, offering valuable insights for the rational design of high-performance catalysts for ammonia decomposition.

催化氨分解是一种高效、环保的制氢途径。镍基催化剂以其成本效益而闻名，已成为贵金属催化剂的有希望的替代品。然而，镍纳米颗粒形态对催化性能的影响尚未得到充分的研究。在这项研究中，我们报道了通过调节金属-载体相互作用在CeO2-Al2O3上构建锥体Ni纳米颗粒。这种创新的方法显著提高了催化效率，在500°C下，在重量小时空间速度为30 000 mL g(cat)−1 h−1下，NH3转化率达到75.62%，同时在连续操作1000小时内保持优异的稳定性。综合表征结合DFT计算表明，锥体镍纳米粒子比球形镍纳米粒子具有更高比例的高配位表面。几何和电子的联合作用降低了d带中心，削弱了Ni-N键，有利于N-N复合，从而加快了反应速率。该研究强调了活性金属形态在控制催化行为中的关键作用，为合理设计高性能氨分解催化剂提供了有价值的见解。

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引用次数: 0

Chloride molten salt-mediated one-step electrochemical recycling of tellurium from copper(i) telluride 氯化物熔盐催化一步电化学回收碲化铜

IF 9.2 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2026-01-22 Epub Date: 2026-01-28 DOI: 10.1039/d5gc06339f

Libo Chen , Jiguo Tu , Meng Zhang , Mingyin Kou , Shuqiang Jiao

Copper(i) telluride (Cu₂Te) derived from the copper smelting process is an important source of tellurium (Te) recovery. However, conventional Te extraction relies on acid and alkaline leaching processes, which generate toxic waste and involve prolonged processing steps. Developing green and efficient Te recycling methods is therefore essential to improve production efficiency, shorten process flow and reduce environmental pollution. In this work, a chloride molten salt-mediated, one-step electrochemical approach for the separation and extraction of Te is proposed. The thermodynamic calculations and molten salt property analysis demonstrate that the molten LiCl–KCl is an ideal mediated electrolyte for Cu₂Te recycling. The electrochemical investigations further confirm that the controlled cathodic Cu reduction and anodic Te oxidation can be achieved at a relatively negative potential (≤−1.7 V vs. AgCl/Ag). The systematic optimization of electrolysis conditions indicates that the complete separation and recovery of Te and Cu are realized by controlling the cell voltage (∼2.4 V), electrolysis temperature (∼420 °C), and duration (≥3 h). Moreover, the purity of Te and atom economy obtained by this method can reach 99.98% and 100%, respectively, with a recovery efficiency of 93.0% and an energy consumption of only ∼1.24 kWh per kg of Te. Compared to traditional hydrometallurgical processes, this proposed approach shortens workflows, reduces Te loss, generates no waste, co-produces high-value metallic Cu and reduces production costs. Ultimately, this work provides a clean, waste-free and sustainable strategy for treating Cu₂Te from spent copper telluride slag.

铜冶炼过程中产生的碲化铜（Cu2Te）是回收碲的重要来源。然而，传统的碲提取依赖于酸和碱浸出过程，这会产生有毒废物，并且涉及长时间的处理步骤。因此，开发绿色高效的回收方法对于提高生产效率、缩短工艺流程和减少环境污染至关重要。本文提出了一种以氯化物熔盐为介质的一步电化学分离提取碲的方法。热力学计算和熔盐性质分析表明，熔融LiCl-KCl是一种理想的Cu2Te回收介质电解质。电化学研究进一步证实，可控的阴极Cu还原和阳极Te氧化可以在相对负电位（≤- 1.7 V vs. AgCl/Ag）下实现。系统优化的电解条件表明，通过控制电池电压（~ 2.4 V）、电解温度（~ 420℃）和电解时间（≥3 h），可以实现Te和Cu的完全分离和回收。此外，该方法获得的Te纯度和原子经济性可分别达到99.98%和100%，回收率为93.0%，每千克Te的能耗仅为~ 1.24 kWh。与传统的湿法冶金工艺相比，该方法缩短了工作流程，减少了Te损失，不产生废物，可共同生产高价值金属Cu，降低了生产成本。最终，本研究为从废碲化铜渣中处理Cu2Te提供了一种清洁、无废物和可持续的策略。

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引用次数: 0

Quaternary ammonium hydroxide-catalyzed methanolysis of bisphenol–A polycarbonate: performance, mechanism, and scale-up 季铵盐催化双酚a型聚碳酸酯的甲醇分解：性能、机理及规模放大

IF 9.2 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2026-01-22 Epub Date: 2026-02-03 DOI: 10.1039/d5gc05255f

Lu Zhang , Li Song , Haipeng Dong , Jing-Bang Kang , Honglu Zhu , YunJin Zhong , Hengcong Tao , Yao-Yao Zhang , Xianming Zhang

Polycarbonate (PC) is extensively utilized in various industrial applications; however, its environmental persistence and inherent difficulties associated with its recycling have raised significant concerns. To address these issues and promote a circular economy, it is crucial to develop efficient and sustainable depolymerization methods. In this study, tetramethylammonium hydroxide (TMAOH) was used as an efficient depolymerization catalyst, exhibiting excellent catalytic activity and selectivity, with satisfactory chromatic properties and eliminating the need for additional catalyst removal. Real-time visual observations, complemented by GPC and DSC analyses, revealed a degradation process marked by a gradual particle size reduction and a decrease in molecular weight. Mechanistic studies using FT-IR, NMR, and GC analyses uncovered two coexisting pathways, each involving distinct carbonate bond cleavage mechanisms. Owing to its advantages such as mild reaction conditions, high activity, and decomposability without residues, the catalytic system was seamlessly implemented at the pilot scale. The process proved scalable (5 kg per batch) and effective for processing waste PC. The recovered bisphenol–A met industrial purity standards (≥99.85%), and the repolymerization from the recovered monomer could offer commercial-grade PC. Life cycle assessment revealed that this process reduces carbon emissions by 63% compared to conventional fossil-based routes, while generating an economic benefit of $911 per ton of PC processed, providing an environmentally and economically sustainable solution for the closed-loop recycling of PC.

聚碳酸酯（PC）广泛应用于各种工业应用；但是，它的环境持久性和与回收利用有关的固有困难引起了重大关注。为了解决这些问题并促进循环经济，开发高效和可持续的解聚方法至关重要。在本研究中，四甲基氢氧化铵（TMAOH）作为高效解聚催化剂，具有优异的催化活性和选择性，具有满意的色性，无需额外的催化剂去除。实时视觉观察，再加上GPC和DSC分析，揭示了一个降解过程，其特征是粒径逐渐减小，分子量逐渐下降。利用FT-IR、NMR和GC分析的机制研究揭示了两种共存的途径，每种途径都涉及不同的碳酸盐键裂解机制。该催化体系具有反应条件温和、活性高、可分解无残留物等优点，在中试规模上得以顺利实施。该工艺被证明是可扩展的（每批5公斤），并有效地处理废弃PC。回收的双酚a达到工业纯度标准（≥99.85%），单体再聚合后可生产工业级PC。生命周期评估显示，与传统的化石燃料路线相比，该工艺减少了63%的碳排放，同时每处理一吨PC产生911美元的经济效益，为PC的闭环回收提供了一种环境和经济上可持续的解决方案。

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引用次数: 0

Solvent-free aerobic oxidation of benzylic C–H bonds via nanoconfined cobalt–porphyrin frameworks: a green and safe catalytic strategy 通过纳米钴卟啉框架无溶剂有氧氧化苯基C-H键：一种绿色和安全的催化策略

IF 9.2 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2026-01-22 Epub Date: 2026-02-03 DOI: 10.1039/d6gc00073h

Hong-liang Ye , Kai-jing Zhang , Yuan-bin She

The solvent-free aerobic oxidation of inert benzylic C–H bonds using molecular oxygen represents an atom-economical and environmentally benign route to high-value oxygenated chemicals. However, conventional approaches often suffer from safety risks associated with radical chain reactions and peroxide accumulation, alongside poor sustainability profiles due to extensive solvent use and stoichiometric oxidants. Herein, we develop three-dimensional cobalt–porphyrin-based porous aromatic frameworks (CoPor-PAFs) synthesized via Suzuki–Miyaura coupling, which serve as efficient heterogeneous catalysts for the selective oxidation of benzylic secondary C–H bonds. The optimized catalyst, CoPor-PAF-4, features highly dispersed Co²⁺ sites, tailored micropores (0.50–0.80 nm), and passivated residual groups via a dual-capping strategy. Under solvent-free conditions, CoPor-PAF-4 achieves 60.1% conversion of p-ethylnitrobenzene with 94.5% selectivity toward p-nitroacetophenone at 130 °C and 1.0 MPa O₂, delivering a high turnover number (TON) of 13,151. More importantly, this system delivers outstanding green metrics, including an E-factor of 0.81 and a reaction mass efficiency (RME) of 55%, significantly outperforming most solvent-dependent and stoichiometric oxidant-based protocols. Integrated mechanistic investigations, combining spectroscopic analysis, kinetic modeling, and DFT calculations, elucidate that the nanoconfined space exerts control by restricting radical diffusion (as quantified by configurational diffusion models) and promoting a low-barrier oxygen-rebound pathway. This unique environment effectively suppresses hazardous peroxyl radical chain reactions. Together, this work establishes a green, efficient, and intrinsically safe catalytic system for C–H oxidation that aligns with key principles of green chemistry, including waste prevention and catalytic efficiency.

利用分子氧对惰性苯基C-H键进行无溶剂好氧氧化，是一种原子经济、环境友好的高价值含氧化学品生产途径。然而，传统方法往往存在与自由基链反应和过氧化物积累相关的安全风险，以及由于广泛使用溶剂和化学计量氧化剂而导致的可持续性差。本研究通过Suzuki-Miyaura偶联制备了三维钴卟啉多孔芳香骨架（CoPor-PAFs），作为苯类仲碳氢键选择性氧化的高效非均相催化剂。优化后的催化剂CoPor-PAF-4具有高度分散的Co2+位点、定制的微孔（0.50-0.80 nm）和通过双封盖策略钝化残留基团的特点。在无溶剂条件下，copol - paf -4在130℃、1.0 MPa O2条件下，对乙基硝基苯的转化率为60.1%，对对硝基苯的选择性为94.5%，周转率（TON）高达13,151。更重要的是，该系统提供了出色的绿色指标，包括0.81的e因子和55%的反应质量效率（RME），显著优于大多数依赖溶剂和基于化学计量氧化剂的方案。综合机理研究，结合光谱分析、动力学建模和DFT计算，阐明了纳米密闭空间通过限制自由基扩散（由构型扩散模型量化）和促进低势垒氧反弹途径发挥控制作用。这种独特的环境有效地抑制了有害的过氧自由基链式反应。总之，这项工作建立了一个绿色、高效、本质安全的碳氢氧化催化系统，符合绿色化学的关键原则，包括废物预防和催化效率。

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引用次数: 0

A hydrophobic ionic liquid and ZIF-8 co-modified graphene oxide membrane for efficient osmotic energy conversion 一种疏水离子液体与ZIF-8共改性氧化石墨烯膜的高效渗透能转换

IF 9.2 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2026-01-22 Epub Date: 2026-02-10 DOI: 10.1039/d5gc06269a

Yizhuo Wang , Changchao Yan , Jingyun Guo , Zhizhen Ye , Xinyi Wan , Xinsheng Peng

Two-dimensional (2D) nanofluidic membranes hold great promise for osmotic energy conversion, yet achieving an optimal balance between ion permeability and selectivity remains a critical challenge. Herein, a spatially confined strategy was employed to in situ grow ZIF-8 nanoparticles and incorporate hydrophobic ionic liquid (HIL) [Bmim][NTf₂] within a laminated graphene oxide (GO) membrane to form a GO/ZIF-8/[Bmim][NTf₂] composite membrane with heterostructured nanochannels. The GO laminates serve as a robust scaffold for the whole system. The in situ growth of ZIF-8 enhances ion permeability and refines selectivity. The incorporation of HIL not only improves the membrane stability in aqueous electrolyte but also forms a continuous medium to optimize the ionic transport environment within the channels. Benefiting from this synergy, the resulting composite membrane achieves an excellent cation selectivity of 0.945 and a power density of 10.4 W m⁻² under a 50-fold NaCl concentration gradient. This strategy is universal for the fabrication of different GO/MOF/HIL composite membranes (such as GO/HKUST-1/[Bmim][NTf₂] and GO/ZIF-8/[Bmim][PF₆]) and provides new insights into the design of high-performance 2D/MOF/HIL composite membranes for osmotic energy conversion.

二维（2D）纳米流体膜在渗透能量转换方面具有很大的前景，但在离子渗透性和选择性之间实现最佳平衡仍然是一个关键的挑战。本文采用空间限制策略原位生长ZIF-8纳米颗粒，并将疏水离子液体（HIL） [Bmim][NTf2]掺入层状氧化石墨烯（GO）膜中，形成具有异质结构纳米通道的GO/ZIF-8/[Bmim][NTf2]复合膜。氧化石墨烯层压板作为整个系统的坚固支架。原位生长的ZIF-8提高了离子渗透性，提高了选择性。HIL的加入不仅提高了膜在水溶液中的稳定性，而且形成了一个连续介质，优化了通道内的离子传输环境。在50倍NaCl浓度梯度下，复合膜的阳离子选择性为0.945，功率密度为10.4 W m−2。该策略适用于制备不同的GO/MOF/HIL复合膜（如GO/ hkst -1/[Bmim][NTf2]和GO/ZIF-8/[Bmim][PF6]），为设计用于渗透能转换的高性能2D/MOF/HIL复合膜提供了新的见解。

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引用次数: 0

Substrate tunnel redesign of short-chain dehydrogenase enabled efficient biocatalytic production of the TRPV1 antagonist trans-4-tert-butylcyclohexanol 短链脱氢酶的底物隧道重新设计使TRPV1拮抗剂反式-4-叔丁基环己醇的高效生物催化生产成为可能

IF 9.2 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2026-01-22 Epub Date: 2026-02-10 DOI: 10.1039/d5gc06523b

Ting Wang , Lidan Ye , Hongwei Yu

trans-4-tert-Butylcyclohexanol (trans-), an antagonist for the transient receptor potential channel vanilloid subfamily member 1 (TRPV1) used in sensitive skin cosmetics, faces sustainability challenges in conventional chemical synthesis. While biocatalytic approaches employing carbonyl reductases offer eco-friendly alternatives, existing enzymes lack sufficient activity and trans-selectivity for this substrate. In this study, an NADH-dependent short-chain dehydrogenase from Escherichia coli K12, UCPA, was identified to exhibit excellent diastereoselectivity (de) and moderate catalytic activity for trans- production. Structure-guided redesign of the substrate tunnel generated a small library of 12 mutants. The top variant, Y187A, achieved a 15.6-fold activity enhancement. When integrated with enzyme-coupled NADH regeneration, this mutant enabled complete conversion of 1 M 4-tert-butylcyclohexanone () to trans- within 10 h, showing both excellent trans-selectivity (>99.9%) and yield (>99.0%). This biocatalyst also demonstrated broad applicability, efficiently reducing five additional para-alky-substituted cyclohexanones to the corresponding trans-alcohols. Molecular dynamics simulations revealed that the activity improvements arose from a widened substrate tunnel, an optimized hydrophobic binding microenvironment, and increased flexibility in the critical loop region. This work establishes a rational tunnel engineering strategy for short-chain dehydrogenases (SDRs) and delivers a robust biocatalyst for sustainable trans- synthesis.

反式-4-叔丁基环己醇（trans-1b）是一种用于敏感皮肤化妆品的瞬时受体电位通道香草蛋白亚家族成员1 （TRPV1）的拮抗剂，在传统化学合成中面临可持续性挑战。虽然采用羰基还原酶的生物催化方法提供了生态友好的替代品，但现有的酶对这种底物缺乏足够的活性和反式选择性。在这项研究中，从大肠杆菌K12中鉴定出一种nadh依赖的短链脱氢酶，UCPA，对反式1b的生产具有优异的非对异选择性（de）和中等催化活性。结构导向的基底隧道重新设计产生了一个包含12个突变体的小库。顶部改型Y187A实现了15.6倍的活性增强。当与酶偶联NADH再生结合时，该突变体能够在10 h内将1 M 4-叔丁基环己酮（1a）完全转化为反式1b，具有优异的反式选择性（>99.9%）和产率（>99.0%）。这种生物催化剂也显示出广泛的适用性，有效地将五个额外的对烷基取代环己酮还原为相应的反式醇。分子动力学模拟表明，活性的提高来自于加宽的底物通道，优化的疏水结合微环境，以及关键环区柔韧性的增加。本研究为短链脱氢酶（SDRs）建立了一个合理的隧道工程策略，并为可持续的反式1b合成提供了一个强大的生物催化剂。

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引用次数: 0

Modulation of hydrogen transfer behaviors over Fe/Cu interfacial sites for a boosted electrocatalytic nitrate reduction reaction 电催化硝酸还原反应中Fe/Cu界面上氢转移行为的调控

IF 9.2 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2026-01-22 Epub Date: 2026-02-03 DOI: 10.1039/d5gc06182b

Hongxia Luo , Lin Gu , Ziyang Wu , Jun Chen , Jianping Yang

An electrocatalytic nitrate reduction reaction (NO₃RR) over Cu-based catalysts represents an energetically feasible route for treating nitrogenous wastewater. However, its efficiency remains limited by the sluggish dissociation of H₂O, which fails to supply active hydrogen (*H) in time to support the hydrogenation of nitrogenous intermediates. Herein, an in situ electrochemical reconstruction strategy is employed to fabricate FeCu-hydroxide nanoarrays directly on copper foam (R-FeCu-OH/CF NAs); owing to the superior hydrogen transfer ability from Fe sites to Cu sites, the synergistic catalytic process (*NO₃ adsorption, *NO₃–*NO₂ and *NO₂ hydrogenation) exhibits favorable thermodynamics. Spectroscopic and theoretical evidence indicates that Fe sites at Fe/Cu interfaces facilitate H₂O dissociation, enabling efficient *H transfer to Cu. This process suppresses NO₂⁻ accumulation and *H coupling, leading to lower energy barriers for NO₃⁻ adsorption and *NO₂/*NO to *NOH. The catalyst achieves up to 92% NO₃⁻ conversion and nearly 100% N₂ selectivity, while providing a stability of up to 60 cycles and a retention of 98%. When deployed as the cathode in a Zn–NO₃⁻ battery, the catalyst delivers an open-circuit voltage of 1.27 V and a peak power density of 9.26 mW cm⁻², outperforming previously reported electrocatalysts. This work elucidates hydrogen-transfer mechanisms and guides the design of efficient electrohydrogenation reactions.

铜基催化剂上的电催化硝酸还原反应（NO3RR）为处理含氮废水提供了一条能量可行的途径。然而，其效率仍然受到H2O解离缓慢的限制，不能及时提供活性氢（*H）来支持含氮中间体的加氢。本文采用原位电化学重构策略直接在泡沫铜（R-FeCu-OH/CF NAs）上制备氢氧化铁纳米阵列；由于优异的氢从Fe位转移到Cu位的能力，使得*NO3吸附、*NO3 - *NO2和*NO2加氢的协同催化过程表现出良好的热力学特性。光谱和理论证据表明，Fe/Cu界面上的Fe位点促进H2O解离，使*H有效转移到Cu。这一过程抑制了NO2−的积累和*H的耦合，导致NO3−吸附和*NO2/*NO到*NOH的能垒降低。该催化剂的NO3 -转化率高达92%，N2选择性接近100%，同时提供了高达60次循环的稳定性和98%的保留率。当作为阴极部署在Zn-NO3−电池中时，该催化剂提供了1.27 V的开路电压和9.26 mW cm−2的峰值功率密度，优于先前报道的电催化剂。这项工作阐明了氢转移机理，并指导了高效电加氢反应的设计。

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引用次数: 0