Molecular Catalysis最新文献_第7页

Biolubricant production from Indian castor seed oil using ethyl biodiesel (2G precursor) and sodium methoxide as a homogeneous catalyst 用乙基生物柴油（2G前驱体）和甲氧二钠作为均相催化剂从印度蓖麻籽油中生产生物润滑剂

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2026-01-02 DOI: 10.1016/j.mcat.2025.115697

Amit Kumar Rajak , Madiga Harikrishna , Prakash Kumar Sarangi , Piotr Prus , Mallampalli S.L. Karuna

This study presents a novel approach to the synthesis of high-performance biolubricants from Indian castor seed oil (ICSO), addressing a key gap in the current literature where most prior research has focused on single-step transesterification or biodiesel applications of castor oil. The research introduces a two-step transesterification strategy that enhances the physicochemical properties of the final product. In the first step, ethanolysis of ICSO was performed to produce Castor fatty acid ethyl esters (CFAEs), with optimized parameters ethanol-to-oil molar ratio of 6:1, 2% H₂SO₄ catalyst, at 65 °C for 60 min yielding high-purity intermediates. These CFAEs were subsequently reacted with 1,1-Tris(hydroxymethyl)propane (TMP) under optimized conditions (1:6 molar ratio, 0.8% sodium methoxide, 120 °C, 90 min) to obtain a triester-based biolubricant with a maximum yield of 85.3%. This dual-step method represents a significant improvement in process efficiency and product performance over conventional approaches. Structural confirmation using FTIR, ¹H NMR, and ¹³C NMR revealed successful esterification and high product purity. The resulting castor biolubricant exhibited a Viscosity Index of 139, Pour Point of −10 °C, and Flash Point of 250 °C values that meet ISO VG 68 specifications, indicating compatibility with commercial industrial lubricant standards. Unlike traditional castor oil modifications, this process enhances thermal stability, positioning the product as a viable, sustainable alternative to mineral-based lubricants. This work contributes a scalable, renewable, and chemically robust pathway for advanced biolubricant production from non-edible feedstocks.

本研究提出了一种从印度蓖麻籽油（ICSO）合成高性能生物润滑剂的新方法，解决了当前文献中大多数先前研究集中于蓖麻油的单步酯交换或生物柴油应用的关键空白。该研究引入了两步酯交换策略，提高了最终产品的物理化学性质。第一步，将ICSO进行醇解制备蓖麻脂肪酸乙酯（CFAEs），优化参数为乙醇与油的摩尔比为6:1，催化剂为2% H₂SO₄，在65℃条件下反应60 min，得到高纯度中间体。这些CFAEs随后与1,1-三（羟甲基）丙烷（TMP）在优化条件下（1:6摩尔比，0.8%甲氧基钠，120℃，90 min）反应，得到三酯基生物润滑剂，最大收率为85.3%。与传统方法相比，这种双步骤方法在工艺效率和产品性能方面有显著改善。通过FTIR，¹H NMR和¹³C NMR的结构验证表明酯化反应成功，产品纯度高。所得到的蓖麻生物润滑剂粘度指数为139，倾点为−10°C，闪点为250°C，符合ISO VG 68规范，表明与商业工业润滑油标准的兼容性。与传统的蓖麻油改性不同，该工艺提高了热稳定性，使产品成为矿物基润滑剂的可行、可持续的替代品。这项工作为从非食用原料生产先进生物润滑剂提供了可扩展、可再生和化学稳健的途径。

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引用次数: 0

Acid-resistant porous carbon shell coated nickel phosphide for the hydrogenation of xanthine intermediate 用于黄嘌呤加氢中间体的耐酸多孔碳壳包覆磷化镍

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-12-31 DOI: 10.1016/j.mcat.2025.115694

Yongfu Niu , Jianhua Guo , Xiaozhen Shi , Ming Su , Shujie Zhu , Guoyi Bai , Xin Wen

Hydrogenation of 1,3-dimethyl-5-nitroso-6-aminouracil (2Me-NAU) to 1,3-dimethyl-5,6-diaminouracil (2Me-DAU) is a pivotal step in xanthine drug synthesis. Residual acidic impurities from the preceding nitrosation step in dilute sulfuric acid severely deactivate conventional Raney nickel catalyst, causing rapid efficiency decay. To address this, for the first time, we developed an acid-resistant porous carbon-coated nickel phosphide catalyst (Ni₂P@C) that effectively prevents Ni leaching during 2Me-NAU hydrogenation, superior to the Reney nickel catalyst. This catalyst achieves a remarkable 97.4 % 2Me-DAU yield under industrially relevant conditions. Comprehensive characterization confirms that an optimally thick carbon shell combined with controlled defect density maintains both high catalytic activity and exceptional stability (>18 cycles in pH 3.05 H₂SO₄), demonstrating its superior acid resistance as well as potential for large-scale application. This work provides a reference for designing acid-resistant non-noble metal catalysts and offers impetus for the green synthesis of xanthine drugs.

1,3-二甲基-5-亚硝基-6-氨基尿嘧啶（2Me-NAU）加氢生成1,3-二甲基-5,6-二氨基尿嘧啶（2Me-DAU）是黄嘌呤类药物合成的关键步骤。稀硫酸亚硝化过程中残留的酸性杂质严重破坏了传统兰尼镍催化剂的活性，导致效率迅速下降。为了解决这个问题，我们首次开发了一种耐酸多孔碳包覆磷化镍催化剂（Ni2P@C），可以有效防止2Me-NAU加氢过程中的Ni浸出，优于Reney镍催化剂。在工业相关条件下，该催化剂达到了97.4%的2Me-DAU收率。综合表征证实，最佳厚度的碳壳与控制缺陷密度相结合，既保持了高催化活性，又保持了优异的稳定性（在pH 3.05 H2SO4中循环18次），证明了其优越的耐酸性能和大规模应用的潜力。本研究为设计耐酸非贵金属催化剂提供了参考，为黄嘌呤类药物的绿色合成提供了动力。

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引用次数: 0

Engineering the structure of satellitic Pt around Ni on Al2O3 to catalyze methane dry reforming with high durability 在Al2O3上设计Ni表面卫星Pt结构，催化高耐久性甲烷干重整

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-12-31 DOI: 10.1016/j.mcat.2025.115695

Shijun Huang , Yu Song , Shansi Zhong , Panpan Chang , Jinshi Dong , Jiaqiang Yang

Ni based catalysts are widely used in dry reforming of methane (DRM) but still face the issue of deactivation caused by sintering and carbon deposition. Pt doped Ni-Al₂O₃ catalyst was found of great durability which kept 100 % conversion of CO₂ over 300 h without detectable loss in activity at 700 °C, while Ni-Al₂O₃ catalyst only maintained ∼10 h at the same condition. It is revealed that Pt and Ni are separately dispersed on Al₂O₃ with the structure of small Pt particles distributing around Ni like satellites. Kinetic experiments, temperature-programmed surface reactions (TPSR) and DFT calculations indicated that CH₄ prefers to dissociatively adsorb on Pt surface but is hard to deeply crack to carbon because of the high energy barriers. As a result, the respective adsorption of CO₂ on Ni and CH_x on Pt surface largely reduced the bear of competitive adsorption and activation of both reactants on individual Ni and thus brought enhanced activity. Additionally, surrounding Pt effectively suppresses the sintering of Ni during reaction.

镍基催化剂在甲烷干重整（DRM）中得到了广泛的应用，但仍然面临着烧结和积碳引起的失活问题。Pt掺杂的Ni-Al2O3催化剂具有很好的耐久性，在700°C下，在300 h内保持100%的CO2转化率，而Ni-Al2O3催化剂在相同条件下仅保持~ 10 h。结果表明，Pt和Ni分别分散在Al2O3上，呈卫星状分布在Ni周围的小Pt颗粒结构。动力学实验、温度程序表面反应（TPSR）和DFT计算表明，CH4倾向于在Pt表面离解吸附，但由于高能量势垒的存在，CH4难以深度裂解为碳。因此，CO2在Ni表面的吸附和CHx在Pt表面的吸附在很大程度上降低了两种反应物对单个Ni的竞争吸附和活化，从而提高了活性。此外，在反应过程中，周围的Pt有效地抑制了Ni的烧结。

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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 : 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

Lanthanide-based perovskites: Photothermal catalysts for highly yield synthesis of licarin a from oxidative homo-coupling of biomass-derived isoeugenol 镧系钙钛矿：生物质源异丁香酚氧化均偶联高效合成licarin a的光热催化剂

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-12-30 DOI: 10.1016/j.mcat.2025.115689

Wenyu Wang, Yaru Liu, Xiang Shao, Yuhao Zheng, Benyong Zhu, Jun Tang, Qiuhong Pan, Qingping Ke

The selective catalytic oxidation of biomass-derived compounds presents a considerable challenge due to the presence of multiple reactive sites. This study introduces a manganese-doped perovskite La_0.5Sr_0.5MnO₃ (LSMn) photothermal catalyst, synthesized using a urea-redox & sol-gel process, to address this challenge. The as-synthesized LSMn catalyst demonstrates remarkable catalytic performance in the photothermal oxidative homo-coupling of isoeugenol to Licarin A under visible light (λ ≥ 420 nm) and mild temperature (75 °C). Under these conditions, the yield of Licarin A exceeds 90%, a substantial improvement relative with conventional thermal catalysis. Kinetics study reveals that the process operates as photothermal co-catalysis process. Mechanistic studies show that superoxide radicals (O₂^•−), generated through activation of O₂ on the LSMn catalyst under visible light irradiation, and the chemisorption of isoeugenol on Mn³⁺ site under the mild temperature synergistically drive the reaction. These reactive intermediates (O₂^•−species and chemisorbed isoeugenol) facilitate the formation of isoeugenol-derived radicals, which undergo intramolecular conjugate addition and deprotonation to produce Licarin A, with H₂O₂ as a by-product. This study not only demonstrates the efficacy of the LSMn catalyst in the efficient activation and conversion of molecular oxygen (O₂) but also provides critical insights into the design of sustainable, non-noble metal-based catalysts for the oxidative valorization of biomass-derived compounds.

由于存在多个反应位点，生物质衍生化合物的选择性催化氧化提出了相当大的挑战。本研究介绍了一种锰掺杂钙钛矿La0.5Sr0.5MnO3 （LSMn）光热催化剂，采用尿素-氧化还原&溶胶-凝胶工艺合成，以解决这一挑战。合成的LSMn催化剂在可见光（λ≥420 nm）和温和温度（75℃）下，对异丁香酚与Licarin A的光热氧化均偶联反应表现出优异的催化性能。在此条件下，Licarin A的收率超过90%，与传统的热催化相比有了很大的提高。动力学研究表明，该过程为光热共催化过程。机理研究表明，可见光照射下LSMn催化剂上O2活化产生的超氧自由基（O2•−）与温和温度下异丁香酚在Mn3+位点上的化学吸附协同驱动反应。这些活性中间体（O2•−和化学吸附的异丁香酚）促进异丁香酚衍生自由基的形成，这些自由基经过分子内共轭加成和去质子化反应生成Licarin A，副产物为H2O2。这项研究不仅证明了LSMn催化剂在分子氧（O2）的有效活化和转化方面的功效，而且为设计可持续的非贵金属基催化剂用于生物质衍生化合物的氧化增值提供了重要的见解。

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引用次数: 0

Structural changes in H-ZSM-5 zeolite induced by selective framework dissolution and their consequences for the catalytic performance in the methanol-to-hydrocarbons reaction 选择性骨架溶解诱导H-ZSM-5分子筛结构变化及其对甲醇-烃反应催化性能的影响

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-12-30 DOI: 10.1016/j.mcat.2025.115693

Livingstone Udofia , Thomas Friederici , Peter Veit , Franziska Scheffler , Michael Schwidder

Traditionally inexpensive alternatives, such as etching and chemical reductions, offer efficient possibilities for creating dual porosity, reorganizing zeolitic phases, and enhancing the accessibility of active species that facilitate hydrocarbon conversions and industrial scale-up. Through a systematic approach, framework dissolution (FD) of an MFI zeolite was investigated to assess its structural characteristics and catalytic performance. N₂ sorption, XRD, solid-state NMR, thermogravimetry, and electron microscopy techniques were employed to examine the impact of FD on the morphological changes. The results suggest that the FD process can selectively create ordered mesoporous systems. However, the total acidities decrease with increasing NaOH concentration. The broad distribution of hydrocarbon (HC) products from the autocatalysis of single-pass methanol showed that BTX accounted for 57 % of the average yield in an aromatic-rich HC base. Meanwhile, C₂–C₄ HCs averaged 15 % over the mesoporous zeolites, significantly favouring a low aromatics-to-olefins selectivity ratio. The variety of products, including p-xylene and olefin selectivity, suggests that controlled FD can extend the zeolite lifespan and regulate hydrogen transfers and cyclization products during C–C bond coupling, by influencing shape-to-pore interconnectivity.

传统的廉价替代方法，如蚀刻和化学还原，为创造双重孔隙、重组沸石相、提高活性物质的可及性提供了有效的可能性，从而促进了碳氢化合物的转化和工业规模的扩大。通过系统的方法，研究了一种MFI分子筛的骨架溶解（FD），以评价其结构特征和催化性能。采用N2吸附、XRD、固体核磁共振、热重、电镜等技术考察FD对形貌变化的影响。结果表明，FD工艺可以选择性地形成有序介孔体系。但随着NaOH浓度的增加，总酸降低。单道甲醇自催化生成的烃（HC）产物分布广泛，表明在富芳HC碱中，BTX占平均产率的57%。与此同时，C2-C4 hc比介孔沸石平均高出15%，明显有利于较低的芳烃-烯烃选择性比。产物的多样性，包括对二甲苯和烯烃的选择性，表明控制FD可以通过影响形状-孔互连性来延长沸石寿命，调节C-C键偶联过程中的氢转移和环化产物。

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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 : 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

Halide-free ionic liquids with dual-regulation of anion nucleophilicity and basicity for the efficient CO2 conversion into cyclic carbonates 具有阴离子亲核性和碱性双重调节的无卤化物离子液体，可有效地将CO2转化为环状碳酸盐

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-12-29 DOI: 10.1016/j.mcat.2025.115682

Wen Liu , Qian Su , Zifeng Yang , Mengqian Fu , Yifan Liu , Weiguo Cheng

The conversion of CO₂ into cyclic carbonates is a feasible approach for CO₂ mitigation. The environmentally friendly halide-free catalysts, which could avoid the waste halide contamination and industrial equipment corrosion are highly concerned. In this study, a series of halide-free ionic liquids with dual regulation of anion basicity and nucleophilicity were designed to achieve high catalytic efficiency. Among the synthesized ionic liquids, the [BmmIm][PA] demonstrated superior catalytic efficiency, delivering 94.9 % product yield with 99.9 % selectivity under the optimized conditions (70 °C, 2 mol%, 3.5 h, 10 bar). According to the deep activation energies analysis, the superior catalytic efficiency of [BmmIm][PA] was attributed to the strong nucleophilicity of [PA] reducing the ring-opening activation energy and the mild basicity of [PA] reducing the ring-closing activation energy simultaneously. The lower reaction activation energy catalyzed by [BmmIm][PA] was further confirmed by kinetic experiments. Finally, by combining DFT calculations with IR, NMR spectroscopy, a detailed catalytic mechanism involving direct epoxides activation by [PA], CO₂ insertion and ring-closing was proposed. This work provided a more comprehensive understanding of halide-free catalysts and laid a theoretical foundation for the green and efficient conversion of CO₂.

将二氧化碳转化为环状碳酸盐是减缓二氧化碳排放的一种可行方法。环保型无卤化物催化剂，可避免废卤化物污染和工业设备腐蚀，受到广泛关注。本研究设计了一系列具有阴离子碱性和亲核性双重调节的无卤化物离子液体，以达到较高的催化效率。在所合成的离子液体中，[BmmIm][PA]表现出优异的催化效率，在优化条件（70℃，2 mol%, 3.5 h, 10 bar）下，产物收率为94.9%，选择性为99.9%。根据深度活化能分析，[BmmIm][PA]的优异催化效率是由于[PA]的强亲核性降低了开环活化能，而[PA]的温和碱性同时降低了闭环活化能。动力学实验进一步证实了[BmmIm][PA]催化的较低反应活化能。最后，通过将DFT计算与IR、NMR光谱相结合，提出了[PA]直接活化环氧化物、CO2插入和环闭合的详细催化机理。这项工作使人们对无卤化物催化剂有了更全面的认识，为CO2的绿色高效转化奠定了理论基础。

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引用次数: 0

Ni-ZnIn2S4 enabled dual-function photocatalysis: high-selective C12 fuels production with simultaneous H2 evolution Ni-ZnIn2S4启用双功能光催化：高选择性C12燃料生产与同时氢气的生成

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-12-29 DOI: 10.1016/j.mcat.2025.115690

Yu Zhang , Xiaolong Li , Wencong Liu , Qianqian Li , Baoan Fan , Lan Yuan

The photocatalytic C-C coupling of biomass-derived 5-hydroxymethylfurfural (HMF) into high-energy-density C₁₂ fuel precursors, coupled with simultaneous H₂ evolution, provides a promising pathway for sustainable energy production. The main challenge lies in achieving high selectivity towards C₁₂ products and efficiently utilizing the photogenerated charge carriers. Herein, we report the construction of Ni-modified ZnIn₂S₄ (Ni-ZIS) composites via a facile in-situ photodeposition strategy for efficient photocatalytic HMF coupling to C₁₂ products with H₂ production under visible light in an anaerobic aqueous medium. The optimal 3Ni-ZIS catalyst achieves 9 times enhanced activity for H₂ evolution and 1.4 times enhanced selectivity for C₁₂ production, as compared to bare ZIS nanosheets. Typically, after 10 h of irradiation, a remarkable H₂ production of 503 μmol·g⁻¹, with a HMF conversion of 46 % and a C₁₂ selectivity of 92 % (C₁₂ yield of almost 42 %) was achieved over 3Ni-ZIS, while demonstrating excellent stability and recyclability. A combination of photoelectrochemical characterizations and in-situ spectroscopic analysis reveals that the deposited Ni cocatalyst not only serves as an active site for proton reduction, significantly boosting H₂ evolution, but also promotes the dehydrogenation of HMF and facilitates the subsequent selective radical coupling pathway towards C₁₂ products. This work provides a synergistic approach for concurrent biomass valorization and renewable hydrogen fuel production, offering valuable insights into the design of multifunctional photocatalysts for complex organic transformations.

生物质衍生的5-羟甲基糠醛（HMF）光催化C-C偶联成高能量密度的C12燃料前体，并伴有同步的H2演化，为可持续能源生产提供了一条有前景的途径。主要的挑战在于实现对C12产物的高选择性和有效地利用光生成的载流子。在此，我们报道了镍改性ZnIn2S4 （Ni-ZIS）复合材料的构建，通过一种简单的原位光沉积策略，在可见光下在厌氧水介质中有效地光催化HMF偶联到C12产物并产生H2。与裸ZIS纳米片相比，优化后的3Ni-ZIS催化剂的H2生成活性提高了9倍，C12生成选择性提高了1.4倍。通常，经过10 h的辐照，3Ni-ZIS的H2产量为503 μmol·g−1，HMF转化率为46%，C12选择性为92% (C12收率接近42%)，同时具有良好的稳定性和可回收性。结合光电化学表征和原位光谱分析表明，沉积的Ni助催化剂不仅作为质子还原的活性位点，显著促进H2的析出，而且还促进了HMF的脱氢，促进了随后的选择性自由基偶联途径生成C12产物。这项工作为生物质增值和可再生氢燃料生产提供了一种协同方法，为复杂有机转化的多功能光催化剂的设计提供了有价值的见解。

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引用次数: 0

Sustainable continuous-flow catalysis and Bayesian optimization of biomass-derived HMF hydrogenation over RuPt@g-C3N4 RuPt@g-C3N4上生物质HMF加氢的持续连续流催化和贝叶斯优化

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-12-28 DOI: 10.1016/j.mcat.2025.115687

Weida Xia , Yuxi Zhan , Jialong Xia , Guihua Luo , Weike Su , Kejie Chai , An Su

2,5-Furandimethanol (BHMF) is a valuable bio-based diol obtained via selective catalytic hydrogenation of 5-hydroxymethylfurfural (HMF). BHMF serves as a key intermediate for synthesizing biodegradable polymers and renewable fuels, supporting the shift toward sustainable chemical production. In this work, we designed the bimetallic RuPt@g-C₃N₄ catalyst to enable continuous-flow selective hydrogenation of HMF. To optimize this process, we employed a data-driven Bayesian optimization framework to efficiently explore the reaction space, encompassing temperature, pressure, and catalyst formulation. Under optimized conditions (152 °C, 1.2 MPa), the RuPt@g-C₃N₄ catalyst exhibited remarkable activity, achieving a 98% HMF conversion and a 95% yield of BHMF. This performance can be attributed to the synergistic effect of the dual-metal active sites, which enhanced molecular hydrogen activation. Additionally, the surface hydrogen transfer effect, facilitated by the metals and the metal-loaded C₃N₄ support, collectively promoted efficient hydrogen activation and strengthened HMF adsorption on the catalyst surface. Furthermore, real-time reaction monitoring was enabled by inline Fourier-transform infrared (FTIR) spectroscopy coupled with partial least squares (PLS) regression. Overall, this integrated approach, which combines machine learning, bimetallic catalysis, and inline FTIR analytics, provides a powerful platform for advancing sustainable catalytic hydrogenation processes.

2,5-呋喃二甲醇（BHMF）是由5-羟甲基糠醛（HMF）选择性催化加氢得到的一种有价值的生物基二醇。BHMF是合成可生物降解聚合物和可再生燃料的关键中间体，支持向可持续化学品生产的转变。在这项工作中，我们设计了双金属RuPt@g-C3N4催化剂来实现HMF的连续流选择性加氢。为了优化这一过程，我们采用了一个数据驱动的贝叶斯优化框架来有效地探索反应空间，包括温度、压力和催化剂配方。在优化条件（152℃，1.2 MPa）下，RuPt@g-C3N4催化剂表现出了显著的活性，HMF转化率达到98%，BHMF产率达到95%。这种性能可归因于双金属活性位点的协同作用，增强了分子氢的活化。此外，金属和负载金属的C3N4载体促进了表面氢转移效应，共同促进了氢的高效活化，增强了HMF在催化剂表面的吸附。此外，通过内联傅里叶变换红外光谱（FTIR）和偏最小二乘（PLS）回归，实现了反应的实时监测。总的来说，这种综合方法结合了机器学习、双金属催化和在线FTIR分析，为推进可持续的催化加氢过程提供了一个强大的平台。

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引用次数: 0