Molecular Catalysis最新文献_第8页

Synthesis of iron nanoparticles for heterogeneous electrocatalytic oxidation of acid orange dye: In situ and stepwise mechanism 非均相电催化氧化酸性橙染料用铁纳米颗粒的合成：原位和分步机理

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2026-03-01 Epub Date: 2026-01-30 DOI: 10.1016/j.mcat.2026.115755

Redae Nuguse Berhe , Martha Dagnew , Juwon Park , Joon Wun Kang , Hyunook Kim

Recent research has been focused on synthesizing iron oxide (Fe₃O₄) nanoparticles (Fe₃O₄ NPs) for wastewater treatment via electrochemical oxidation. In this study, Fe₃O₄ NPs of various sizes were synthesized from iron chloride salts (Fe₃O₄ NPs-C), iron sulfate salts (Fe₃O₄ NPs-S) and a mixture of both salts (Fe₃O₄ NPs-M). The effect of pH and anionic strength of each salt precursor on the size distribution of Fe₃O₄ NPs (C, S, and M) was investigated. The synthesized Fe₃O₄ NPs were characterized using several techniques to analyze their physio-chemical properties. Field emission-scanning electron microscope (FE-SEM) and vibrating sample magnetometer analysis of Fe₃O₄ NPs (C, S, and M) revealed average hydrodynamic diameter of 23, 17 and 48 nm, with saturation magnetization of 76 ± 2.4, 79 ± 2.6 and 66 ± 2.8 emu g^-1, respectively. Dispersed Fe₃O₄ NPs were prepared from each Fe₃O₄ NPs (C, S, and M), achieving catalytic oxidation efficiencies for Acid Orange 7 (AO7) of 89.4 ± 1.7%, 93.2 ± 1.5% and 83.7 ± 2.3%, respectively. At optimal operating conditions, 97.8 ± 1.4% oxidation efficiency was obtained over 40 min using Fe₃O₄ NPs-S heterogenous electrode. Finally, the regeneration efficiency of Fe₃O₄ NPs-S was found to be 54.3 ± 2.8% after seven consecutive cycles, demonstrating the potential of these synthesized heterogenous dispersed Fe₃O₄ NPs for efficient and reusable electrocatalytic oxidation of organic pollutants.

电化学氧化法制备氧化铁纳米颗粒（Fe3O4 NPs）用于废水处理是近年来研究的热点。在本研究中，以氯化铁盐（Fe3O4 NPs- c）、硫酸铁盐（Fe3O4 NPs- s）和两种盐的混合物（Fe3O4 NPs- m）合成了不同尺寸的Fe3O4 NPs。考察了不同盐前驱体的pH和阴离子强度对Fe3O4 NPs （C、S、M）粒径分布的影响。采用多种技术对合成的Fe3O4 NPs进行了表征，分析了其理化性质。场发射扫描电镜（FE-SEM）和振动样品磁强计分析显示，Fe3O4纳米粒子（C、S和M）的平均水动力直径分别为23、17和48 nm，饱和磁化强度分别为76±2.4、79±2.6和66±2.8 emu g-1。用C、S、M三种Fe3O4 NPs制备了分散的Fe3O4 NPs，对酸性橙7 （AO7）的催化氧化效率分别为89.4±1.7%、93.2±1.5%和83.7±2.3%。在最佳操作条件下，Fe3O4 NPs-S非均相电极在40 min内的氧化效率为97.8±1.4%。经过连续7次循环后，Fe3O4 NPs- s的再生效率为54.3±2.8%，证明了这些合成的异质分散Fe3O4 NPs具有高效、可重复使用的电催化氧化有机污染物的潜力。

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引用次数: 0

Engineering of FeS/NiS nanocomposites using biomass-derived carbon support to modulate spin polarization and catalytic properties 利用生物质衍生碳载体调节自旋极化和催化性能的FeS/NiS纳米复合材料工程

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2026-03-01 Epub Date: 2026-01-30 DOI: 10.1016/j.mcat.2026.115749

Prashant K. Bhartiya , Manish Srivastava , Debabrata Mishra

In this work, a chiral molecule-overlay FeS/NiS nanocatalyst supported by rice husk ash (RHA) derived graphene like carbon nanosheets (GLCN) is synthesized and electrochemically evaluated on a nickel foam (NiF) substrate for effective hydrogen evolution reactions (HER) and oxygen evolution reactions (OER). An abundant agricultural biowaste, RHA-derived GLCN makes it an eco-friendly alternative to expensive catalysts, which improves the stability and surface area of the catalyst by acting as a durable and porous support matrix. The assimilation of chiral coatings induces chiral-induced spin selectivity (CISS), which enhances both HER and OER performance. From electrochemical study, in alkaline conditions, the NiF-FeS/NiS/GLCN hybrid electrode with chiral molecules coating provides a remarkable overpotential of -109 mV for HER at -20 mAcm^-2 and 290 mV for OER at 20 mAcm^-2. The combined advantages of conductive FeS/NiS/GLCN active sites and spin-polarization effects provided by chiral coatings are responsible for this prominent enhancement in current density (

\sim 3 - f o l d

) both in OER & HER. The findings pave the way for the development of next-generation electrocatalysts that use sustainable materials and novel surface modifications to achieve effective energy conversion in water splitting applications.

在这项工作中，合成了一种手性分子覆盖的FeS/NiS纳米催化剂，该催化剂由稻壳灰（RHA）衍生的石墨烯类碳纳米片（GLCN）支撑，并在泡沫镍（NiF）衬底上进行了电化学评价，以进行有效的析氢反应（HER）和析氧反应（OER）。作为一种丰富的农业生物废弃物，rhaa衍生的GLCN使其成为昂贵催化剂的环保替代品，它作为一种耐用的多孔支撑基质，提高了催化剂的稳定性和表面积。手性涂层的同化作用诱导了手性诱导自旋选择性（CISS），提高了HER和OER性能。电化学研究表明，在碱性条件下，手性分子包覆的NiF-FeS/NiS/GLCN杂化电极在-20 mAcm-2下的过电位为-109 mV，在20 mAcm-2下的过电位为290 mV。导电FeS/NiS/GLCN活性位点的综合优势和手性涂层提供的自旋极化效应是OER和HER中电流密度显著增强（约3 -倍）的原因。这一发现为下一代电催化剂的开发铺平了道路，这些电催化剂使用可持续材料和新的表面修饰，在水分解应用中实现有效的能量转换。

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引用次数: 0

Unraveling the catalytic role of Fe2/Cu(111) diatomic sites in selective CO2 electroreduction to ethanol 揭示Fe2/Cu（111）双原子位在选择性CO2电还原制乙醇中的催化作用

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2026-03-01 Epub Date: 2026-01-30 DOI: 10.1016/j.mcat.2026.115750

Yilei Zhou, Zhiyuan Yang, Liyun Jiang, Qi Yu

In this work, density functional theory (DFT) is employed to explore the full reaction landscape of CO₂ reduction to C₂ species on Fe₂ diatomic sites supported by Cu(111) (Fe₂/Cu(111) DAC). Compared with the Fe single-atom catalyst (Fe₁/Cu(111) SAC), Fe₂/Cu(111) DAC shows stronger *CO₂ adsorption, promotes subsequent proton-coupled electron transfer (PCET) steps. Notably, the C-C coupling via *HCO-*HCOO is thermodynamically favorable (ΔG = 0.67 eV), and its kinetic feasibility is further evaluated by transition-state calculations. This pathway bypasses the HCOOH-forming route and suggests a preference toward CH₃CH₂OH. Electronic structure analysis reveals the underlying mechanism for CO₂ activation and C-C coupling.

本文采用密度泛函理论（DFT）研究了Cu（111）负载的Fe2双原子位（Fe2/Cu(111) DAC）上CO2还原为C2的完整反应过程。与Fe单原子催化剂（Fe1/Cu(111) SAC）相比，Fe2/Cu(111) DAC表现出更强的*CO2吸附，促进了后续质子耦合电子转移（PCET）步骤。值得注意的是，通过*HCO-*HCOO的C-C耦合在热力学上是有利的（ΔG = 0.67 eV），并且通过过渡态计算进一步评估了其动力学可行性。该途径绕过hcooh形成途径，并倾向于CH3CH2OH。电子结构分析揭示了CO2活化和碳-碳耦合的潜在机制。

引用次数: 0

Sustainable conversion of biogenic citronellal to cis-p-menthane-3,8-diol via tailored Cr-doped sulfonated biochar catalyst 通过定制的铬掺杂磺化生物炭催化剂可持续地将生物香茅醛转化为顺式对甲烷-3,8-二醇

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2026-03-01 Epub Date: 2026-01-29 DOI: 10.1016/j.mcat.2026.115735

Prashant Kumar , Priyabrat Mohapatra , Chandan Singh Chanotiya , Mohd Faizan Husain , Himmat Singh , Narayan Prasad Yadav , Suresh Kumar Bhargava , Selvakannan Periasamy , Ylias Sabri , Prasant Kumar Rout

p-Menthane-3,8-diol (PMD) is a bio-derived mosquito repellent valued for its low toxicity and environmental safety compared to synthetic alternatives such as DEET. Here, we report a sustainable catalytic pathway for the selective semi-synthesis of PMD from citronellal-rich essential oils using Cr-functionalized sulfonated biochar (Cr-SBC-HT) derived via hydrothermal carbonization. The tailored 5 %Cr-SBC-HT catalyst delivered 99 % conversion of citronellal and 96.7 % selectivity towards cis-PMD (cis/trans ratio 93:7) under mild conditions (60 °C, 85 min, 15 wt % catalyst). The catalyst exhibited robust structural integrity and reusability across ten cycles, underpinned by detailed physicochemical characterization (XRD, FT-IR, BET, TGA, SEM, HRTEM, XPS). Process optimization using response surface methodology (RSM)-box behnken design (BBD) further improved efficiency. The methodology demonstrated excellent green metrics, with a Process mass intensity (PMI) of 1.045, Turnover number (TON) of 386, Turnover frequency (TOF) of 272 h⁻¹, and an E-factor of 0.045. The enriched cis-PMD has displayed mosquito repellency for up to 6 h against Aedes species, confirming its practical application. This study highlighted the role of biomass-derived catalysts in enabling scalable, durable, and environmentally benign chemical manufacturing, bridging green materials development with bioactive product synthesis.

对甲基甲烷-3,8-二醇（PMD）是一种生物衍生的驱蚊剂，与避蚊胺等合成替代品相比，它具有低毒和环境安全的优点。在这里，我们报道了一种可持续的催化途径，利用水热碳化衍生的cr功能化磺化生物炭（Cr-SBC-HT），从富含香茅醛的精油中选择性半合成PMD。定制的5% Cr-SBC-HT催化剂在温和的条件下（60°C， 85分钟，15 wt %的催化剂），香茅醛的转化率为99%，顺式pmd的选择性为96.7%（顺反比93:7）。通过详细的物理化学表征（XRD, FT-IR， BET， TGA， SEM， HRTEM， XPS），该催化剂表现出坚固的结构完整性和可重复使用性。采用响应面法(RSM)-盒氏设计（BBD）的工艺优化进一步提高了效率。该方法证明了良好的绿色指标，过程质量强度（PMI）为1.045，周转数（TON）为386，周转频率（TOF）为272 h⁻¹，e因子为0.045。富集的顺式pmd对伊蚊的驱蚊效果长达6小时，证实了其实际应用价值。这项研究强调了生物质衍生催化剂在实现可扩展、耐用和环保的化学制造方面的作用，将绿色材料开发与生物活性产品合成联系起来。

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引用次数: 0

Unraveling pore-dependent metal–support interactions in CuO/SiO2 catalysts for low-temperature reverse water–gas shift catalysis CuO/SiO2催化剂中孔依赖性金属-载体相互作用的低温逆水气转换催化研究

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2026-02-15 Epub Date: 2025-12-29 DOI: 10.1016/j.mcat.2025.115691

Thanapha Numpilai , Nutkamaithorn Polsomboon , Napaphut Dolsiririttigul , Wanwisa Limphirat , Waleeporn Donphai , Anusorn Seubsai , Metta Chareonpanich , Thongthai Witoon

This study investigates the structure–activity relationship of Cu/SiO₂ catalysts for the reverse water–gas shift (RWGS) reaction, focusing on how silica pore size and silanol density govern Cu dispersion, redox behavior, and catalytic performance. Mesoporous silica supports with average pore sizes of 2.1–11.0 nm were synthesized by sol–gel synthesis at different pH values and subsequently impregnated with 10–15 wt% Cu. Structural characterization (N₂ sorption, XRD, TEM, and EXAFS) revealed that small pores and high silanol density enhanced Cu dispersion but also stabilized Cu²⁺ species and strongly bound CO₂, while large pores with low silanol density promoted Cu aggregation and weakened metal–support interactions. H₂-TPD and CO₂-TPD analyses showed that catalysts with intermediate pore sizes provided both accessible metallic Cu⁰ sites for H₂ activation and abundant Cu–O–Si interfacial sites for CO₂ chemisorption. Among the series, 10Cu/S-3.9 achieved the highest CO₂ conversion (8.4%) with an optimal balance between dispersion, reducibility, and product desorption, while also demonstrating excellent long-term stability (9.8% conversion after 50 h, 100% CO selectivity). Apparent activation energies (66–84 kJ mol^-1) further correlated with the interplay of pore structure, silanol density, and Cu–support interaction. These findings establish pore-size and silanol engineering as an effective strategy to tune Cu structure and guide the rational design of efficient Cu-based RWGS catalysts.

本研究研究了Cu/SiO2催化剂在逆向水气转换（RWGS）反应中的构效关系，重点研究了二氧化硅孔径和硅醇密度对Cu分散、氧化还原行为和催化性能的影响。在不同的pH值下，采用溶胶-凝胶法合成了平均孔径为2.1 ~ 11.0 nm的介孔二氧化硅载体，并浸渍了10 ~ 15 wt%的Cu。结构表征（N2吸附、XRD、TEM和EXAFS）表明，小孔隙和高硅醇密度增强了Cu的分散，同时也稳定了Cu2+物种和强结合的CO2，而低硅醇密度的大孔隙促进了Cu的聚集，减弱了金属负载相互作用。H2- tpd和CO2- tpd分析表明，中等孔径的催化剂为H2活化提供了可接近的金属Cu0位点，并为CO2化学吸附提供了丰富的Cu-O-Si界面位点。其中，10Cu/S-3.9在分散、还原性和产物脱附之间达到最佳平衡，实现了最高的CO2转化率（8.4%），同时也表现出优异的长期稳定性（50 h后转化率为9.8%，100% CO选择性）。表观活化能（66 ~ 84 kJ mol-1）与孔结构、硅烷醇密度和cu -负载相互作用进一步相关。这些发现表明，孔径和硅醇工程是调整Cu结构的有效策略，并指导高效Cu基RWGS催化剂的合理设计。

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引用次数: 0

Chemoenzymatic synthesis of mirabegron using an engineered styrene monooxygenase 利用工程苯乙烯单加氧酶化学酶合成米拉贝隆

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2026-02-15 Epub Date: 2025-12-27 DOI: 10.1016/j.mcat.2025.115686

Bingrong Chen , Saili Xu , Qidong Pan , Rongchuan Hong , Wei Zhu , Xiaoxia Liu , Miaolin Ke , Zhiran Ju , Fener Chen

A highly efficient chemo-enzymatic approach has been developed for the synthesis of mirabegron-a selective β₃-adrenergic receptor agonist indicated for overactive bladder treatment. Starting from styrene, an engineered styrene monooxygenase (SMO) catalyzes the critical epoxidation step, yielding the key chiral intermediate with excellent enantioselectivity (>99 % ee) and a moderate yield of 36 %. This enzymatic process obviates the need for intermediate isolation and reduces the use of toxic reagents, offering distinct advantages over traditional chemical synthesis in terms of sustainability and atom economy. Subsequent eco-friendly chemical transformations of the intermediate afford mirabegron. This optimized protocol, which is efficient and scalable, achieves a final mirabegron yield of 17.7 %, underscoring the potential of enzymatic systems for the efficient synthesis of this therapeutic agent.

已经开发了一种高效的化学-酶方法来合成miraberon -一种选择性β₃-肾上腺素能受体激动剂，用于治疗膀胱过度活跃症。以苯乙烯为原料，利用SMO催化环氧化反应，得到了对映选择性优异（99% ee）、产率适中（36%）的关键手性中间体。这种酶催化过程避免了中间分离的需要，减少了有毒试剂的使用，在可持续性和原子经济性方面比传统化学合成具有明显的优势。随后中间体的环保化学转化提供了mirabegron。该优化方案高效且可扩展，最终的mirabegron产率达到17.7%，强调了酶系统有效合成这种治疗剂的潜力。

引用次数: 0

(Chloroformyl)acetates as a key platform molecule for converting chloroacetic acid to high-end chemicals （氯甲酰基）醋酸酯是氯乙酸转化为高端化学品的关键平台分子

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2026-02-15 Epub Date: 2025-12-19 DOI: 10.1016/j.mcat.2025.115670

Bo Zhao , Yujia Liu , Jing Li , Guoquang Tang , Babak Kaboudin , Jianbin Li , Yanlong Gu

To find a new approach to converting chloroacetic acid, which was oversupplied in the market recently, to value-added chemicals, ethyl (chloroformyl)acetate 1a was proposed as a downstream platform molecule because of its easy synthesis and multiple reactivity. A catalytic system for Feist-Bénary reaction between 1a and 1,3-dicarbonyl compound was established, which opened efficient way for the synthesis of various trisubstituted furan derivatives. A selective C3-alkenylation reaction of indole with 1a was also established in the presence of an acid catalyst. All these new findings on the reactivity of 1a greatly enrich molecular diversity of the downstream products of 1a, laying the foundation for it to serve as a key platform molecule for the high-value conversion of chloroacetic acid.

为了寻找一种新的途径，将目前市场上供过于求的氯乙酸转化为高附加值化学品，由于氯甲酰乙酸乙酯1a易于合成且具有多重反应性，因此被提出作为下游平台分子。建立了1a与1,3-二羰基化合物feist - b化学反应的催化体系，为合成各种三取代呋喃衍生物开辟了有效途径。在酸性催化剂的作用下，吲哚与1a发生了选择性的c3 -烯基化反应。这些关于1a反应性的新发现，极大地丰富了1a下游产物的分子多样性，为其作为氯乙酸高值转化的关键平台分子奠定了基础。

引用次数: 0

MOF-constrained Rh enables stable in situ H2O2 supply for peroxide-dependent enzymes mof约束的Rh使过氧化氢依赖酶的原位H2O2供应稳定

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2026-02-15 Epub Date: 2026-01-08 DOI: 10.1016/j.mcat.2026.115702

Yutong Wang , Chunyu Huang , Jelco Albertsma , Monique van der Veen , Miguel Alcalde , Frank Hollmann

Peroxide-dependent enzymes often suffer from irreversible oxidative deactivation by the peroxide co-substrate. Transition metal mediated in situ generation of H₂O₂ offers continuous peroxide feeding in low concentration. However, free metal complexes often interact non-selectively with proteins, leading to mutual deactivation of metal catalysts and enzymes. Here, we report a spatial isolation strategy using zirconium-based metal-organic frameworks (UiO-67) to immobilize the transition metal catalytic unit [Cp*Rh(bpy)Cl]⁺. The porous MOF structure acts as a molecular sieve, excluding enzymes from the Rh sites on the framework, thus protecting both catalysts from mutual deactivation. The Rh modified UiO-67 (Rh@UiO-67) catalyzes the flavin-mediated electron transfer from formate to oxygen, generating H₂O₂ in a formate oxidase mimicking fashion. Its protein compatibility allows Rh@UiO-67 to fuel peroxyzymes for stable oxyfunctionalization. Compared to natural formate oxidase, this system also shows high stability to various pH and temperatures, enabling its application in versatile conditions.

过氧化物依赖酶常常受到过氧化物共底物的不可逆氧化失活。过渡金属介导的原位生成H2O2在低浓度下提供连续的过氧化物供给。然而，游离金属配合物经常与蛋白质非选择性地相互作用，导致金属催化剂和酶的相互失活。在这里，我们报道了一种利用锆基金属有机框架（UiO-67）固定过渡金属催化单元[Cp*Rh(bpy)Cl] +的空间隔离策略。多孔MOF结构充当分子筛，将酶从框架上的Rh位点排除，从而保护两种催化剂免于相互失活。Rh修饰的UiO-67 （Rh@UiO-67）催化黄素介导的电子从甲酸到氧的转移，以模仿甲酸氧化酶的方式产生H2O2。它的蛋白质相容性允许Rh@UiO-67为过氧酶提供稳定的氧功能化燃料。与天然甲酸氧化酶相比，该体系在各种pH值和温度下都表现出很高的稳定性，使其能够在各种条件下应用。

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引用次数: 0

Engineered acidic porosity of glauconite-sulfonated polystyrene (G/SPS) composite for selective catalytic cracking of waste oil to biofuel 海绿石-磺化聚苯乙烯（G/SPS）复合材料选择性催化裂化废油制备生物燃料的工程酸性孔隙

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2026-02-15 Epub Date: 2025-12-30 DOI: 10.1016/j.mcat.2025.115684

Doaa A. Khalifa , Abdelrahman M. Rabie , Elsayed A. Elsharaky , Doaa I. Osman , Omayma F. Abdel-Gawad , Sayed A. Ahmed

The catalytic cracking (CC) of sunflower waste cooking oils (SFWCOs) provides an alternative to nonrenewable fuels. A novel composite catalyst was developed by combining natural glauconite clay with synthetic sulfonated recycled polystyrene polymer (G/SPS) for CC of SFWCO. The G/SPS catalyst was analyzed using XRD, FTIR, BET surface area, TGA, and NH₃-TPD. XRD shows that SPS coats G clay particles, reducing polymer aggregation and forming well-organized quasi-crystals on the materials surface. TGA analysis shows that the catalyst maintains stability up to 350 °C without decomposing the sulfonic group. NH₃-TPD analysis reveals both moderate and strong acid sites on the synthetic composite. Various parameters, including temperature and catalyst concentration, were studied. The results indicated a maximum conversion of 98.8% and a 91.66% yield when the catalyst weight was 0.6% of the SFWCO weight and the temperature was 340 °C. The biofuels produced satisfying ASTM specifications for both physical and chemical properties. Distillation and gas chromatography (GC) of the organic liquid products (OLPs) displayed that the selectivity towards hydrocarbons in the C8-C14 range (bio jet) made up 41.3%, while those in the C12-C24 range (diesel-range hydrocarbons) comprised 58.7%. The catalytic activity and reaction mechanism were explained using GC–MS analysis. The catalyst remained stable and effective over six cycles, producing biofuel with properties close to international standards.

向日葵废食用油的催化裂化（CC）为不可再生燃料提供了一种替代方法。以天然海绿石粘土与合成磺化再生聚苯乙烯聚合物（G/SPS）为催化剂，研制了一种新型复合催化剂。采用XRD、FTIR、BET比表面积、TGA和NH3-TPD对G/SPS催化剂进行了分析。XRD结果表明，SPS包覆G粘土颗粒，减少了聚合物聚集，在材料表面形成组织良好的准晶体。TGA分析表明，该催化剂在350℃下保持稳定，不分解磺酸基。NH3-TPD分析显示合成的复合材料上有中酸性和强酸位点。研究了温度和催化剂浓度等参数。结果表明，当催化剂质量为SFWCO质量的0.6%，反应温度为340℃时，转化率为98.8%，收率为91.66%。生产的生物燃料在物理和化学性能方面都符合美国材料试验协会的规范。有机液体产物（OLPs）的蒸馏和气相色谱（GC）表明，C8-C14范围（生物射流）的选择性为41.3%，C12-C24范围（柴油范围）的选择性为58.7%。用GC-MS分析了催化活性和反应机理。该催化剂在六个循环中保持稳定和有效，生产出的生物燃料性能接近国际标准。

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引用次数: 0

Hydrodearomatization deceleration as a key factor of improved selectivity in transfer hydrogenation of phenolics over Ni-Co bifunctional catalysts 加氢脱芳减速是提高酚类化合物在镍钴双功能催化剂上转移加氢选择性的关键因素

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2026-02-15 Epub Date: 2026-01-09 DOI: 10.1016/j.mcat.2026.115711

Damir Nasokhov, Alexey Philippov, Nikolay Nesterov, Vera Pakharukova, Igor Prosvirin, Oleg Martyanov

The study aims to control the selectivity towards hydrodeoxygenation (HDO) products in the transfer hydrogenation of guaiacol and anisole by decelerating aromatic ring saturation, using isopropanol as a hydrogen donor. For this purpose, bifunctional Ni-Co catalysts were synthesized using an eco-friendly method based on coprecipitation in supercritical CO₂. The bifunctionality of the bimetallic catalysts was achieved through the controlled replacement of some nickel with cobalt, a metal that is known to have lower activity in the saturation of aromatic rings. The peculiarities of the synthesized samples are high content of the active compound and monophasic bimetallic particles, which facilitates interaction between Ni and Co. It was observed that the rate of aromatic ring saturation decreased as nickel was substituted for cobalt in the catalyst. Simultaneously, the rate constants of anisole and guaiacol HDO responded differently to cobalt substitution. The hydrogenolysis of the COMe bond in guaiacol accelerated with higher Co content. In contrast, for anisole, the elimination of the same fragment, catalyzed by bimetallic catalysts, slowed down compared to the monometallic Ni sample. Importantly, the approach of slowing hydrodearomatization proved versatile, as this effect was observed for both anisole and guaiacol with an increase in Co content. Thus, this work demonstrates the design of catalysts capable of processing real lignin pyrolysis oil, which is rich in a diverse set of oxygenated molecules.

以异丙醇为给氢体，通过降低芳环饱和度来控制愈伤木酚和苯甲醚转移加氢反应中对氢脱氧产物的选择性。为此，采用超临界CO2共沉淀法合成了双功能Ni-Co催化剂。双金属催化剂的双功能是通过用钴取代镍来实现的，钴是一种已知在芳环饱和中活性较低的金属。合成样品的特点是活性化合物和单相双金属颗粒含量高，有利于Ni和Co之间的相互作用。结果表明，在催化剂中镍取代钴后，芳环饱和速率降低。同时，苯甲醚和愈创木酚HDO的速率常数对钴取代反应的响应不同。愈创木酚中COMe键的氢解速度随Co含量的增加而加快。相比之下，对于苯甲醚，在双金属催化剂的催化下，与单金属Ni样品相比，相同片段的消除速度要慢。重要的是，减缓加氢脱芳的方法被证明是通用的，因为随着Co含量的增加，这种效果对苯甲醚和愈创木酚都有观察到。因此，这项工作证明了催化剂的设计能够处理真正的木质素热解油，它富含多种氧化分子。

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引用次数: 0