Molecular Catalysis最新文献_第9页

Hydrothermal temperature-regulated interface effects in Ce@Mn core-shell catalysts for efficient formaldehyde removal 水热温度调节的Ce@Mn核壳催化剂的界面效应对甲醛的高效去除

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-12-20 DOI: 10.1016/j.mcat.2025.115669

Dan Chen , Kan Li , Hanyue Bao , Ming Zhai , Zhong Wang , Xiaozhi Wang

In this paper, a series of Ce@Mn core-shell catalysts were synthesized via a two-step hydrothermal method. Hydrothermal temperature significantly influenced the structure formation of catalysts. The Ce@Mn-150 catalyst, synthesized at 150 °C exhibited a well-defined core-shell structure. Moreover, it converted approximately 35 % of HCHO into CO₂ and H₂O at ambient temperature, and achieved 90 % conversion of HCHO at 90 °C. Through structural characterization of the catalysts, distinct morphological differences were observed across all samples. The Ce@Mn-150 catalyst, which demonstrated the optimal catalytic activity, exhibited the most complete core-shell structure. The formation of the core-shell structure promoted the generation of Ce-Mn interfacial effects, which in turn modulated the interactions between Ce and Mn species. Elemental valence state characterization revealed that the well-defined core-shell structure facilitated the generation of Mn³⁺ and Ce³⁺ species, along with enhanced concentrations of surface-adsorbed oxygen (O_ads) and oxygen vacancies (O_v), which collectively enhanced HCHO adsorption and activation. H₂-TPR results indicated that the core-shell structure enhanced the low-temperature reducibility of the catalyst and preserved abundant oxygen vacancies. This study revealed the influence of core-shell structures and intermetallic interactions at the core-shell interface on the catalytic performance of the catalyst, providing insights for designing efficient non-noble metal catalysts for HCHO removal.

本文采用两步水热法合成了一系列Ce@Mn核壳催化剂。水热温度对催化剂的结构形成有显著影响。在150℃下合成的Ce@Mn-150催化剂具有明确的核壳结构。此外，在室温下，约35%的HCHO转化为CO2和H2O，在90℃下，HCHO的转化率达到90%。通过催化剂的结构表征，在所有样品中观察到明显的形态差异。Ce@Mn-150催化剂具有最完整的核壳结构，具有最佳的催化活性。核壳结构的形成促进了Ce-Mn界面效应的产生，从而调节了Ce和Mn之间的相互作用。元素价态表征表明，明确的核壳结构促进了Mn3+和Ce3+的生成，同时表面吸附氧（Oads）和氧空位（Ov）浓度的增加，共同增强了HCHO的吸附和活化。H2-TPR结果表明，核壳结构增强了催化剂的低温还原性，并保留了丰富的氧空位。本研究揭示了核壳结构和核壳界面金属间相互作用对催化剂催化性能的影响，为设计高效去除HCHO的非贵金属催化剂提供了思路。

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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 : 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

Synergistic mechanism of Ce/P Co-doping in broadening temperature window and enhancing chlorine resistance of VW/Ti catalysts: An integrated experimental and machine learning study Ce/P共掺杂对VW/Ti催化剂增宽温度窗和增强抗氯性的协同机制：实验与机器学习的综合研究

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-12-19 DOI: 10.1016/j.mcat.2025.115661

Jiaojiao Liu, Qiulin Wang, Xiongfei Qi, Haonan Wang, Jing Jin, Dunyu Liu

The challenges of a narrow temperature window (300–400 °C) and low chlorine poisoning resistance limit conventional vanadium catalysts in waste incineration flue gas. This study developed novel Ce/P-codoped VW/Ti catalysts for high-performance low-temperature operation under chlorine-containing atmospheres. By combining multiscale characterization with machine learning analysis, the role of Ce/P doping in enhancing the low-temperature SCR performance, broadening the operating temperature window and strengthening the HCl resistance of catalyst was investigated. The results demonstrated that the developed 2PCe_0.5-VW/Ti catalyst not only achieves stable NO_x conversion of >99 % across a wide 150–450 °C temperature range but also exhibits excellent resistance to chlorine poisoning. The characterization results reveal a synergistic effect between Ce and P doping. On one hand, moderate Ce doping primarily created abundant oxygen vacancies, which facilitate the low-temperature SCR activity and enhance resistance to HCl/H₂O poisoning. On the other hand, H₃PO₄ treatment optimizes the metal valence states and stabilizes the active sites, effectively preventing catalyst deactivation at high temperatures. GBR-based SHAP analysis of 11 input features identified the key activity determinant and revealed the following order of importance: HCl concentration > reaction time > reaction temperature > H₃PO₄ impregnation solution concentration > Ce doping amount. Furthermore, the SHAP-based interpretation quantitatively reveals the directional impacts of these factors. By integrating experimental datasets with interpretable machine learning, this work establishes a data-driven framework that not only delivers a reliable predictive model but also elucidates the governing factors and their influence trends, thereby providing actionable insights for the optimization of SCR catalytic systems.

窄温度窗（300-400°C）和低抗氯中毒能力的挑战限制了传统钒催化剂在垃圾焚烧烟气中的应用。本研究开发了一种新型的Ce/ p共掺杂VW/Ti催化剂，用于含氯气氛下的高性能低温操作。采用多尺度表征和机器学习分析相结合的方法，研究了Ce/P掺杂在提高低温SCR性能、拓宽工作温度窗口和增强催化剂耐HCl性能方面的作用。结果表明，所制备的2PCe0.5-VW/Ti催化剂不仅在150 ~ 450℃的温度范围内实现了99%的稳定NOx转化率，而且具有优异的抗氯中毒性能。表征结果表明Ce和P掺杂之间存在协同效应。一方面，适量的Ce掺杂主要产生了丰富的氧空位，有利于SCR的低温活性，增强了对HCl/H2O中毒的抗性。另一方面，H3PO4处理优化了金属价态，稳定了活性位点，有效防止了催化剂在高温下失活。基于gbr的11个输入特征的SHAP分析确定了关键的活性决定因素，其重要性依次为：HCl浓度>；反应时间>；反应温度>； H3PO4浸渍液浓度>； Ce掺杂量。此外，基于shap的解释定量地揭示了这些因素的定向影响。通过将实验数据集与可解释的机器学习相结合，本研究建立了一个数据驱动的框架，该框架不仅提供了可靠的预测模型，还阐明了控制因素及其影响趋势，从而为SCR催化系统的优化提供了可操作的见解。

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引用次数: 0

Effects of metal-oxide interaction on the CO2 hydrogenation performance of CoAlPtMo catalysts 金属-氧化物相互作用对CoAlPtMo催化剂CO2加氢性能的影响

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-12-18 DOI: 10.1016/j.mcat.2025.115662

Linjun Wang , Qingsong Hu , Xiaolu Xu , Ruiyan Sun , Jie Ren , Chalachew Mebrahtu , Tuo Ji , Zhenchen Tang , Huanhao Chen , Feng Zeng

Enhancing selectivity toward value-added products remains a major challenge in CO₂ hydrogenation. In this study, we systematically tune metal-oxide interactions in Mo-modified CoAlPt catalysts by varying the Co/Al ratio to shift product selectivity from methane toward methanol. A series of Co_xAl₁₋_x catalysts (x = 0.9 to 0.1) were synthesized via co-precipitation followed by Mo incorporation through ion exchange. Lowering the Co/Al ratio strengthens metal-oxide interactions, resulting in reduced crystallite sizes, increased surface areas, as well as enhanced H and CO₂ adsorption strength. These changes suppress deep hydrogenation, favoring methanol formation via the *CH_xO intermediate, resulting in an increased methanol selectivity over methane. Although stronger interactions slightly reduce the intrinsic CO₂ conversion activity, the resulting smaller particles provide a greater number of active sites, effectively compensating this limitation. Among the prepared catalysts, the Co_0.1Al_0.9 catalyst exhibits outstanding performance, achieving a methanol productivity of 1201 μmol g_Pt+Co+Mo⁻¹ h⁻¹ and a CO-free alcohol selectivity of 83.9 %. Accordingly, this work presents a rational approach to tailoring metal–oxide interactions to suppress methane formation and enhance methanol selectivity in CO₂ hydrogenation.

提高对高附加值产品的选择性仍然是二氧化碳加氢的主要挑战。在这项研究中，我们通过改变Co/Al比率，系统地调整mo修饰的CoAlPt催化剂中的金属氧化物相互作用，将产物选择性从甲烷转向甲醇。采用共沉淀法，通过离子交换掺入Mo，合成了一系列x = 0.9 ~ 0.1的CoxAl1−x催化剂。降低Co/Al比增强了金属与氧化物的相互作用，从而减小了晶粒尺寸，增加了表面积，增强了H和CO2的吸附强度。这些变化抑制了深度氢化，有利于通过*CHxO中间体形成甲醇，从而增加了甲醇对甲烷的选择性。虽然更强的相互作用会略微降低固有的二氧化碳转化活性，但产生的更小的颗粒提供了更多的活性位点，有效地补偿了这一限制。在所制备的催化剂中，Co0.1Al0.9催化剂表现出优异的性能，其甲醇产率为1201 μmol gPt+Co+Mo−1 h−1，Co -free醇选择性为83.9%。因此，这项工作提出了一种合理的方法来调整金属-氧化物相互作用，以抑制甲烷的形成，并提高二氧化碳加氢过程中甲醇的选择性。

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引用次数: 0

Charge transfer mechanism in Z-scheme ternary heterojunction photocatalysts of AgCl/CoWO4/Ag and its role in enhancing photocatalytic performance AgCl/CoWO4/Ag三元异质结光催化剂的电荷转移机理及其在提高光催化性能中的作用

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-12-16 DOI: 10.1016/j.mcat.2025.115667

Junlong Zhang , Jie Wei , Long Yang , Ao Cao , Zehao Sun , Youxin Yuanfeng , Xuyu Shen , Bing Chen , Guogang Chen

With the rapid advancement of modern industry and population growth, unrestrained discharge of industrial effluent and domestic sewage has caused severe environmental pollution, which poses a severe challenge to human habitat. Owing to the unique eco-friendly characteristics, photocatalytic technology has emerged as a highly promising approach in the wastewater treatment very recently. Z-scheme heterojunction ternary photocatalysts of “x·AgCl/y·CoWO₄/Ag” were ingeniously designed and developed in this study, exhibiting exceptionally high photocatalytic activity for degrading micropollutants in wastewater compared with single-component photocatalysts. For instance, photocatalytic activity of AgCl/CoWO₄/Ag (reflected by the reaction kinetic parameter k) is 7.7 times that of AgCl and 313 times that of CoWO₄, respectively. The experimental results and analysis revealed a typical Z-scheme charge transfer mechanism in these ternary photocatalyst heterojunctions, thereby confirming the structural characteristics of Z-scheme heterojunction. Furthermore, the ternary photocatalysts retained the reaction activity with virtually no change after undergoing five cycles of catalytic experiments, highlighting its excellent stability. Consequently, an underlying mechanism was proposed herein to account for the enhanced photocatalytic properties. It is believed that such ternary Z-scheme heterojunction materials expand halide-based heterojunction construction methods and promise significant implications for environmental remediation.

随着现代工业的飞速发展和人口的增长，工业废水和生活污水的肆意排放造成了严重的环境污染，对人类栖息地构成了严峻的挑战。光催化技术由于其独特的生态友好性，近年来在污水处理中成为一种很有前途的方法。本研究巧妙地设计和开发了“x·AgCl/y·coo₄/Ag”的z型异质结三元光催化剂，与单组分光催化剂相比，对废水中微污染物的降解具有异常高的光催化活性。例如，AgCl/CoWO₄/Ag的光催化活性（由反应动力学参数k反映）分别是AgCl的7.7倍和CoWO₄的313倍。实验结果和分析揭示了这些三元光催化剂异质结中典型的Z-scheme电荷转移机制，从而证实了Z-scheme异质结的结构特征。此外，三元光催化剂在经过5个循环的催化实验后，其反应活性几乎没有变化，显示出其良好的稳定性。因此，本文提出了一种潜在的机制来解释光催化性能的增强。认为这种三元z型异质结材料扩展了卤化物异质结的构建方法，对环境修复具有重要意义。

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引用次数: 0

Stabilization of amano-lipase using freeze-dried inulin–lipase complex 用冻干菊糖-脂肪酶络合物稳定天冬酰胺脂肪酶

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-12-16 DOI: 10.1016/j.mcat.2025.115658

Yoshiro Tahara, Ryo Tsumura, Michiaki Matsumoto

Lipase is an enzyme that catalyzes unique reactions and has attracted attention for its suitability for use in a wide range of applications. In this study, the addition of sugars, including monosaccharides and polysaccharides, to improve the stability of lipase during freeze-drying was investigated. Among the sugar–lipase complexes investigated, the inulin–lipase complex showed relatively high lipase activity in both aqueous and organic solvents. The inulin–lipase complex also exhibited relatively high lipase residual activities following heat treatment (80 °C over several hours and 50 °C over several weeks), indicating high thermostability and the possibility of long-term storage of lipase. Among the investigated sugars, inulin is a promising stabilizer of lipase during freeze-drying.

脂肪酶是一种催化独特反应的酶，因其广泛的应用前景而备受关注。在本研究中，研究了添加单糖和多糖对提高脂肪酶冷冻干燥稳定性的影响。在研究的糖-脂肪酶配合物中，菊粉-脂肪酶配合物在水溶剂和有机溶剂中均表现出较高的脂肪酶活性。经过热处理（80°C数小时和50°C数周）后，菊粉-脂肪酶复合物也显示出相对较高的脂肪酶残留活性，表明高热稳定性和脂肪酶长期储存的可能性。在所研究的糖类中，菊粉是一种很有前途的脂肪酶冷冻干燥稳定剂。

引用次数: 0

The structure sensitivity of formic acid oxidation on Pt3M alloy: A first principles study 甲酸氧化对Pt3M合金结构敏感性的第一性原理研究

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-12-16 DOI: 10.1016/j.mcat.2025.115666

Cheng Liu , Xuejing Yang , Huiling Guo , Haiming Huang

Platinum, while most active for formic acid oxidation (FAO), suffers from CO poisoning. Alloying Pt improves performance, but rational catalyst design is hindered by limited atomic-scale mechanistic understanding. This study employs density functional theory to systematically investigate FAO on four types of Pt₃M (M = 11 transition metals) surfaces: (111), (110), (100), and Pt-skin/Pt₃M(111). We computed free energy diagrams and onset potentials at low potentials. Results show the direct oxidation path is optimal on all surfaces under these conditions. Electronic structure analysis reveals that the d-band center (εd) of surface Pt atoms shifts upward toward the Fermi level with increasing atomic number of the solute metal M, while the εd of subsurface M atoms shifts oppositely, collectively modulating the adsorption behavior of key intermediates. Among the 47 surfaces studied, 15 surpass Pt(111) in both direct FAO activity and CO tolerance. Notably, nine catalysts including Pt₃Fe(111), Pt₃Ag(110), Pt(100) and Pt₃Ag@Pt(111) are identified as promising candidates. On these surfaces, formic acid preferentially oxidizes via the HCOO intermediate, which effectively prevents potential CO poisoning. Using G_CO* and G_OH* as descriptors, we constructed reaction phase diagrams, revealing activity trends for the indirect pathway across potentials. Analysis shows the relative values of G_CO* and G_OH* determine the indirect pathway's potential-determining step. An ideal catalyst requires moderate OH* adsorption combined with weak CO* adsorption. Based on this, Pt₃Fe(110), Pt₃Co(110), Pt₃Ni(110), Pt₃Cu(110), and Pt₃Cu@Pt(111) were identified as outstanding for FAO at intermediate potentials.

铂虽然对甲酸氧化（FAO）最具活性，但会导致一氧化碳中毒。合金化Pt提高了性能，但合理的催化剂设计受到有限的原子尺度机理理解的阻碍。该研究采用密度泛函理论系统地研究了四种类型的Pt₃M（M = 11种过渡金属）表面上的FAO:（111）、（110）、（100）和Pt-skin/Pt₃M（111）。我们计算了低电位下的自由能图和起始电位。结果表明，在这些条件下，直接氧化路径在所有表面上都是最优的。电子结构分析表明，随着溶质金属M原子序数的增加，表面Pt原子的d带中心（εd）向费米能级向上移动，而亚表面M原子的εd则相反，共同调节了关键中间体的吸附行为。在研究的47个表面中，15个表面的直接FAO活性和CO耐受性都超过了Pt（111）。值得注意的是，Pt₃Fe（111）、Pt₃Ag（110）、Pt₃（100）、Pt₃Ag@Pt（111）等9种催化剂被确定为候选催化剂。在这些表面上，甲酸优先通过HCOO中间体氧化，这有效地防止了潜在的CO中毒。利用GCO*和GOH*作为描述符，我们构建了反应相图，揭示了跨电位间接通路的活性趋势。分析表明，GCO*和GOH*的相对值决定了间接途径的电位决定步骤。理想的催化剂需要适度的OH*吸附和弱的CO*吸附。在此基础上，Pt₃Fe（110）、Pt₃Co（110）、Pt₃Ni（110）、Pt₃Cu（110）和Pt₃Cu@Pt（111）被确定为在FAO中具有优异的中间潜力。

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引用次数: 0

Selective cleavage of ether bond in lignin to cyclohexanones over HCl-promoted Pd/ZrO2 catalyst 在盐酸促进的Pd/ZrO2催化剂上木质素醚键选择性裂解环己酮

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-12-16 DOI: 10.1016/j.mcat.2025.115665

Qun Yu , Wen Zhao , Bingqing Wei , Lei Nie , Zhenglong Li

Cyclohexanone, a key precursor for bio-nylon production, holds significant potential for sustainable synthesis via the catalytic valorization of lignin's aromatic structure. Despite progress in lignin conversion enabling the selective production of compounds like cyclohexanols and hydrocarbons, achieving high selectivity for cyclohexanone remains a significant challenge due to the difficulty in controlling selective hydrogenation of the benzene ring. In this study, we demonstrate that Pd/ZrO₂ catalyzes the conversion of the lignin model compound diphenyl ether (DPE) through a controlled pathway involving several steps: partial hydrogenation, hydrolysis and selective hydrogenation. With the assistance of trace HCl (430 ppm), cyclohexanone is obtained as the primary product with a maximum yield of 82.1 %. The exceptional performance of the Pd/ZrO₂ catalyst in the presence of HCl is attributed to a synergistic mechanism, whereby the Brønsted acid (H⁺) and the oxophilic ZrO₂ support work in concert to activate and cleave CO bonds, while the chloride ions (Cl⁻) fine-tune the Pd nanoparticles to selectively stabilize the ketone intermediate against over-hydrogenation, collectively ensuring high conversion and cyclohexanone selectivity. The reaction pathways leading to high cyclohexanone yields (50–98.5 %) exhibit significant variation depending on the specific ether bond types (4-O-5, α-O-4 and β-O-4) present in the model compounds. Distinct transformation routes observed for different lignin-derived linkages demonstrate that both the reaction pathways and their mechanistic foundations are strongly influenced by the particular CO bond configurations. These findings highlight the critical influence of substrate structure in determining product selectivity.

环己酮是生物尼龙生产的关键前体，通过木质素芳香结构的催化增值，具有可持续合成的巨大潜力。尽管木质素转化在选择性生产环己醇和碳氢化合物方面取得了进展，但由于难以控制苯环的选择性加氢，实现环己酮的高选择性仍然是一个重大挑战。在这项研究中，我们证明了Pd/ZrO2催化木质素模型化合物二苯基醚（DPE）的转化通过一个受控的途径，包括几个步骤：部分加氢、水解和选择性加氢。在微量盐酸（430 ppm）的辅助下，得到环己酮为主要产物，收率最高达82.1%。在HCl存在下，Pd/ZrO2催化剂的优异性能归因于协同机制，其中Brønsted酸（H +）和亲氧的ZrO2载体协同工作，激活和切割CO键，而氯离子（Cl−）微调Pd纳米颗粒，选择性地稳定酮中间体，防止过氢化，共同确保高转化率和环已酮选择性。模型化合物中特定的醚键类型（4-O-5、α-O-4和β-O-4）不同，导致高环己酮产率（50 - 98.5%）的反应途径也有显著差异。观察到不同木质素衍生键的不同转化途径，表明反应途径及其机理基础都受到特定CO键构型的强烈影响。这些发现突出了底物结构对决定产物选择性的关键影响。

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引用次数: 0

Development of l-threonine-immobilized gels and their catalytic properties for asymmetric aldol reaction l-苏氨酸固定化凝胶的研制及其对不对称醛醇反应的催化性能

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-12-15 DOI: 10.1016/j.mcat.2025.115664

Hideaki Tokuyama , Yuto Ishida , Yuna Kamikawa , Tara Fujita , Aika Takeshima , Taichi Kano

Organocatalytic reactions are considered reliable and practical methods for asymmetric syntheses owing to their ease of operation, mild reaction conditions, and environmental friendliness. Heterogeneous catalysts, in which amino acids are immobilized on insoluble supports, have been developed and used in asymmetric aldol reactions. Accordingly, in this study, a novel l-threonine-immobilized gel is developed as a heterogeneous catalyst for the solvent-free asymmetric aldol reactions of various ketones (major components) with 4-nitrobenzaldehyde. An l-threonine derivative monomer is synthesized, and copolymer gels comprising this monomer and a primary monomer are synthesized via free-radical copolymerization. l-Threonine does not exhibit any catalytic activity because of its insolubility in ketone solvents, whereas l-threonine-immobilized gels and l-threonine derivative monomers exhibit good reaction characteristics (yield, stereoselectivity, and chemoselectivity). The apparent reaction rates using millimeter-sized gels (heterogeneous catalysts with easy handling) are comparable to those using l-threonine derivative monomers (homogeneous catalysts), owing to the excellent diffusion permeability toward a range of substances that are characteristic of well-swollen gels. l-Threonine-immobilized gels that absorb the substrate ketone well and absorb water moderately are promising heterogeneous catalysts; that is, an appropriate primary monomer exhibiting such absorption properties must be selected for gel synthesis.

有机催化反应具有操作简单、反应条件温和、环境友好等优点，被认为是不对称合成的可靠而实用的方法。非均相催化剂是一种将氨基酸固定在不溶性载体上的催化剂，已被开发并用于不对称醛醇反应。因此，本研究开发了一种新型的l-苏氨酸固定化凝胶，作为多种酮（主要成分）与4-硝基苯甲醛无溶剂不对称醛醇反应的非均相催化剂。合成了一种l-苏氨酸衍生物单体，并通过自由基共聚合成了包含该单体和原单体的共聚物凝胶。由于l-苏氨酸在酮类溶剂中不溶解，因此它不具有任何催化活性，而l-苏氨酸固定化凝胶和l-苏氨酸衍生物单体具有良好的反应特性（产率、立体选择性和化学选择性）。使用毫米大小的凝胶（易于处理的多相催化剂）的表观反应速率与使用l-苏氨酸衍生物单体（均相催化剂）的表观反应速率相当，因为它们对一系列具有良好膨胀凝胶特征的物质具有良好的扩散渗透性。l-苏氨酸固定化凝胶吸附底物酮较好，吸水适中，是很有前景的多相催化剂；也就是说，必须选择具有这种吸收特性的合适的原生单体进行凝胶合成。

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引用次数: 0

Enhancing CO2 hydrogenation to methanol over Cu/MnO/ZrO2 catalysts: Unraveling the synergistic effects of Mn promotion Cu/MnO/ZrO2催化剂促进CO2加氢制甲醇：揭示Mn促进的协同效应

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-12-13 DOI: 10.1016/j.mcat.2025.115652

Yunfei Han , Saipeng Zhou , Lei Chen , Yuxia Chen , Zuobo Yang , Jimmy Yun , Jie Zhang , Hong Zhao

The hydrogenation of CO₂ to methanol is a promising solution for reducing CO₂ emissions, but the lack of efficient and stable copper-based catalysts highlights the urgent need for further development in this area. In this study, new copper-manganese-zirconium (Cu/MnO/ZrO₂, CMZ) catalysts with different ratios were designed and prepared by the co-precipitation method, among which the catalyst with a molar ratio of Cu/Mn/Zr elements of (5/2/2) was the most effective. The CMZ catalysts performs CO₂ conversion of 17.6 % and methanol selectivity of 87.2 % at 5 MPa, 250 °C. Combined with XRD, XPS, H₂-TPR and CO₂-TPD, it was confirmed that the introduction of Mn element effectively inhibited the agglomeration of Cu particles and promoted the dispersion of active sites. Enhanced CO₂ adsorption and activation through the formation of a synergistic Cu-MnO-ZrO₂ interface. This study provides theoretical basis and technical support for the resource utilization of CO₂ and the industrial production of green methanol.

二氧化碳加氢制甲醇是减少二氧化碳排放的一种很有前途的解决方案，但缺乏高效和稳定的铜基催化剂突出了该领域进一步发展的迫切需要。本研究采用共沉淀法设计并制备了不同配比的铜锰锆（Cu/MnO/ZrO2， CMZ）催化剂，其中Cu/Mn/Zr元素摩尔比为（5/2/2）的催化剂效果最好。在5mpa， 250℃条件下，CMZ催化剂的CO2转化率为17.6%，甲醇选择性为87.2%。结合XRD、XPS、H2-TPR和CO2-TPD证实，Mn元素的引入有效抑制了Cu颗粒的团聚，促进了活性位点的分散。通过形成Cu-MnO-ZrO2协同界面增强CO2吸附和活化。本研究为CO2资源化利用和绿色甲醇工业化生产提供了理论依据和技术支持。

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引用次数: 0