Journal of Catalysis最新文献_第3页

Construction of a copper-bismuth catalyst featuring Bi-N4 sites and synergistic Bi clusters derived from TCPP(Bi)@HKUST-1 for enhanced formaldehyde to butynediol 构建具有 Bi-N4 位点和 TCPP（Bi）@HKUST-1 衍生的协同 Bi 簇的铜铋催化剂，以提高甲醛制丁炔二醇的效果

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2024-11-10 DOI: 10.1016/j.jcat.2024.115843

Yong Wang , Yongkang Sun , Fusheng Huang , Tingting Wang , Bin Dai , Jichang Liu , Jiangbing Li , Xuhong Guo

The construction of functional catalysts that efficiently catalyze in a reducing atmosphere is considered rather challenging. In this study, the catalysts bridged by Bi-N₄ between copper and bismuth species were prepared. Herein, Bi-N₄ and bismuth cluster sites were incorporated into porous carbon–nitrogen networks along with copper nanoparticles (Bi_SAC&Clu-Cu-NC). For the synthesis, metalloporphyrin-modified HKUST-1 (TCPP(Bi)@HKUST-1) was employed as a precursor. Additionally, metalloporphyrin functioned as a capping agent during catalyst preparation, thereby enhancing the dispersion of Bi species after calcination. Notably, the Bi_SAC&Clu-Cu-NC catalyst demonstrated 93.8 % selectivity towards 1,4-butynediol over 20 h at a Bi loading of 0.6 wt% in a reducing atmosphere of acetylene and formaldehyde. Furthermore, a mechanistic model is proposed that elucidates the observed synergistic catalytic behavior based on experimental characterization and DFT calculations. This proposed model is termed “Nanoparticles with Cluster and Single Metal Sites”(NCS mechanism). The retention of the Bi cluster structure within the material matrix plays a pivotal role in enhancing the adsorption and activation of formaldehyde. Interfacial effects between different copper species favour the activation of the reaction substrate acetylene. Additionally, the Bi-N₄ structure can function as a crucial conduit, facilitating electron transfer between Cu and Bi elements and consequently lowering the activation energy barrier for key reaction intermediates.

构建能在还原气氛中有效催化的功能催化剂是一项相当具有挑战性的工作。本研究制备了铜和铋之间由 Bi-N4 桥接的催化剂。在这种催化剂中，Bi-N4 和铋团簇位点与铜纳米颗粒（BiSAC&Clu-Cu-NC）一起被纳入多孔碳氮网络。在合成过程中，采用了金属卟啉修饰的 HKUST-1 （TCPP(Bi)@HKUST-1）作为前体。此外，金属卟啉在催化剂制备过程中起到了封盖剂的作用，从而提高了煅烧后铋物种的分散性。值得注意的是，在乙炔和甲醛还原气氛中，BiSAC&Clu-Cu-NC 催化剂在 20 小时内对 1,4-丁炔二醇的选择性达到 93.8%，Bi 的负载量为 0.6 wt%。此外，还根据实验表征和 DFT 计算提出了一个机理模型，以阐明所观察到的协同催化行为。该模型被称为 "具有团簇和单金属位点的纳米颗粒"（NCS 机制）。在材料基质中保留 Bi 簇结构对增强甲醛的吸附和活化起着关键作用。不同铜种之间的界面效应有利于活化反应底物乙炔。此外，Bi-N4 结构还可以作为一个重要的通道，促进铜和 Bi 元素之间的电子转移，从而降低关键反应中间产物的活化能垒。

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引用次数: 0

Dealuminated H–Y zeolites generate, stabilize and catalytically insert carbenes from diazocarbonyl compounds 脱铝 H-Y 沸石从重氮羰基化合物中生成、稳定和催化插入烯碳化合物

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2024-11-08 DOI: 10.1016/j.jcat.2024.115835

Yongkun Zheng, Miguel Espinosa, Marta Mon, Antonio Leyva–Pérez

Carbenes are among the most powerful reactants in organic synthesis, with capacity to insert into a variety of otherwise stable bonds, and generate two new bonds in a straightforward manner. However, the intrinsic instability of such carbenes makes them to be catalytically generated, in–situ, from precursors such as diazocarbonyl compounds, and the catalyst, in turn, also controls the subsequent insertion reaction. The catalyst is generally a metal complex in solution, mainly Cu, Ag or Rh, but also others, including protons in rare cases. Here we show that carbenes are generated, stabilized and inserted into C–C, C–H, O–H, N–H, Si–H and O–O bonds after reacting diazocarbonyl compounds with catalytic amounts of metal–free, commercially available dealuminated H–Y zeolites. These results open the way to design carbene–mediated organic reactions on readily available and reusable catalytic solids without involving metals.

烯碳化合物是有机合成中最强大的反应物之一，能够插入各种原本稳定的键中，并以直接的方式生成两个新键。然而，由于这些碳烯的内在不稳定性，它们需要在原位由重氮羰基化合物等前体催化生成，而催化剂反过来也控制着随后的插入反应。催化剂通常是溶液中的金属复合物，主要是铜、银或铑，也有其他金属，包括极少数情况下的质子。在这里，我们展示了在重氮羰基化合物与催化量的无金属、市售脱铝 H-Y 沸石反应后，碳烯的生成、稳定和插入 C-C、C-H、O-H、N-H、Si-H 和 O-O 键。这些结果为在不涉及金属的情况下，在随时可用且可重复使用的催化固体上设计碳介导的有机反应开辟了道路。

引用次数: 0

Facilitating the electrooxidation of 5-hydroxymethylfurfural on nickel hydroxide through deintercalation 通过脱插层促进 5-羟甲基糠醛在氢氧化镍上的电氧化作用

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2024-11-08 DOI: 10.1016/j.jcat.2024.115830

Yu-Feng Qi , Kai-Yao Wang , Hairui Guo , Yu-Jie Zhang , Yiwei Zhou , Cheng Wang

The electrocatalytic of 5-hydroxymethylfurfural oxidation reaction (HMFOR) is an alternative route for the green production of valuable oxygenated chemicals. Nickel hydroxides, which consist of hydroxide layers and interlayer charge-balancing anions, are a type of promising catalysts for HMFOR. Progresses have been made on elucidating the correlation between the hydroxide layer and HMFOR performance, while the effect of intercalated anions on the activity remains unclear. Herein, two self-supported nickel hydroxide catalysts (i.e., pristine Ni(OH)₂/CP-F and deintercalated Ni(OH)₂/CP-A) are employed for revealing the relationship between anion-deintercalation and HMFOR activity. Physical characterizations demonstrate that the deintercalation phenomenon can alter the d-band center and increase the electron density of the Ni site. This endows the deintercalated Ni(OH)₂/CP-A with improved electrochemical properties (conversion = 99.99 %; FDCA yield > 99 %; FE > 99 %), enhanced adsorption strength for HMF, and increased intrinsic activity, compared to the pristine Ni(OH)₂/CP-F. This work not only reports an excellent HMFOR electrocatalyst, but also manifests the crucial effect of deintercalation on the electrochemical oxidation performance of Ni(OH)₂.

电催化 5-羟甲基糠醛氧化反应（HMFOR）是绿色生产有价值含氧化学品的另一条途径。氢氧化镍由氢氧化物层和层间电荷平衡阴离子组成，是一种很有前景的 HMFOR 催化剂。在阐明氢氧化物层与 HMFOR 性能之间的相关性方面已经取得了进展，但插层阴离子对活性的影响仍不清楚。本文采用两种自支撑氢氧化镍催化剂（即原始 Ni(OH)2/CP-F 和脱插层 Ni(OH)2/CP-A）来揭示阴离子脱插与 HMFOR 活性之间的关系。物理特性分析表明，脱插现象可以改变 d 带中心并增加镍位点的电子密度。与原始 Ni（OH）2/CP-F 相比，这使得去交联的 Ni（OH）2/CP-A 具有更好的电化学性能（转化率 = 99.99 %；FDCA 产率 > 99 %；FE > 99 %）、更强的 HMF 吸附强度和更高的内在活性。这项研究不仅发现了一种性能优异的 HMFOR 电催化剂，还揭示了脱夹层对 Ni(OH)2 电化学氧化性能的重要影响。

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引用次数: 0

Facilitating catalytic research via better data reporting and curation: A case study of propane dehydrogenation on Ga/H-ZSM-5 通过更好的数据报告和整理促进催化研究：Ga/H-ZSM-5 上丙烷脱氢的案例研究

IF 7.3 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2024-11-08 DOI: 10.1016/j.jcat.2024.115838

Zhaoqi Zhao, Bingjun Xu

In the field of experimental heterogeneous catalysis, the generation, analysis, and curation of large-scale, high-quality datasets are crucial yet challenging. This work highlights the significance of proper data reporting and curation through a case study on propane dehydrogenation over Ga/H-ZSM-5 catalysts. We demonstrate the challenges and benefits of analyzing larger datasets across multiple publications in the identification of active structures and elucidation of reaction mechanisms. The findings highlight the need for reporting reliable datasets in accessible format to facilitate integration and comparison of catalytic data across different studies, potentially leading to novel scientific insights.

在实验异相催化领域，大规模、高质量数据集的生成、分析和整理至关重要，但也极具挑战性。本研究通过对 Ga/H-ZSM-5 催化剂上丙烷脱氢反应的案例研究，强调了正确报告和整理数据的重要性。我们展示了在确定活性结构和阐明反应机理的过程中，分析多个出版物上的大型数据集所带来的挑战和益处。研究结果强调了以可访问的格式报告可靠数据集的必要性，以促进不同研究中催化数据的整合和比较，从而可能带来新的科学见解。

引用次数: 0

Influence of alumina on the performance of Ag/ZnO based catalysts for carbon dioxide hydrogenation 氧化铝对基于 Ag/ZnO 的二氧化碳氢化催化剂性能的影响

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2024-11-06 DOI: 10.1016/j.jcat.2024.115837

Paul Maurice Leidinger , Vitaly L. Sushkevich , Chiara Pischetola , Frank Krumeich , Jeroen A. van Bokhoven , Luca Artiglia

We study silver-zinc oxide type catalysts with and without the addition of alumina and perform structural analysis and activity tests for the hydrogenation of carbon dioxide. Adding alumina has a dispersing effect on the zinc oxide without structurally altering the silver phase. An alumina-surface enriched ZnO/Al₂O₃ phase is observed with an increased surface reducibility. Ag/ZnO has a high selectivity towards carbon monoxide (63 ± 12 %) and methane (24 ± 3 %) and low selectivity towards methanol (13 ± 0.5 %). Operando infrared (SSITKA-FTIR) and mass spectrometric product detection indicate methane formation via an adsorbed carbon monoxide (CO_ads) intermediate. The selectivity changes gradually with increasing alumina content, up to 80 ± 3 % toward methanol, and 20 ± 4 % carbon monoxide without methane detection, combined with a tripling of the space time yield to 0.65 ± 0.02 mmol_MeOH*

g_{c a t}^{- 1}

*h⁻¹ at 250 °C and 30 bar. Kinetic analysis suggests that the selectivity change originates from hindering the CO-pathway, while the formate pathway leading to methanol remains active.

我们研究了添加和不添加氧化铝的银氧化锌型催化剂，并进行了结构分析和二氧化碳氢化活性测试。添加氧化铝对氧化锌有分散作用，但不会改变银相的结构。观察到氧化铝表面富集的氧化锌/Al2O3 相，其表面还原性增加。氧化铝/氧化锌对一氧化碳（63 ± 12 %）和甲烷（24 ± 3 %）的选择性较高，而对甲醇（13 ± 0.5 %）的选择性较低。操作红外（SSITKA-FTIR）和质谱产品检测表明，甲烷是通过吸附的一氧化碳（COads）中间体形成的。随着氧化铝含量的增加，选择性逐渐发生变化，在 250 °C 和 30 bar 条件下，对甲醇的选择性高达 80 ± 3 %，而对一氧化碳的选择性为 20 ± 4 %，但未检测到甲烷，同时空间产率增加了两倍，达到 0.65 ± 0.02 mmolMeOH*gcat-1*h-1。动力学分析表明，选择性变化源于一氧化碳途径受阻，而甲酸途径导致甲醇仍然活跃。

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引用次数: 0

Theoretical investigation on propane dehydrogenation over extraframework Ga hydride species trapped at Al-pairs in MFI zeolite 框架外氢化镓物种被困在 MFI 沸石中的铝对上进行丙烷脱氢的理论研究

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2024-11-04 DOI: 10.1016/j.jcat.2024.115834

Zhe Feng, Xin Liu, Changgong Meng

Ga/ZSM-5 is widely used to catalyze propane dehydrogenation (PDH). For the harsh operation conditions, the detailed active species, and the plausible reaction pathways that are responsible for the observed superior PDH performance remain unresolved for Ga/ZSM-5. Reduced extraframework Ga hydride species trapped at zeolite framework Al-pairs, including ^b[GaH]²⁺, [Ga]⁺-BAS, [GaH₂]⁺-BAS, etc. are an important kind of Ga species known as active species for PDH. In this work, the PDH pathways these over these Ga species were investigated theoretically at temperatures and pressures relevant to experiments. We showed that dynamically generated undercoordinated ^b[GaH]²⁺ would exhibit significantly higher catalytic activity at PDH conditions as compared with other Ga hydride species. The most plausible PDH pathway over ^b[GaH]²⁺ is the carbenium pathway. The Ga species and BAS act in concert in promoting the H₂ elimination and β-H transfer, and in turning PDH efficient. Ga hydride species may also form as intermediates along the PDH pathways as active sites for subsequent activation and conversion of propane, suggesting the evolution of Ga hydride species trapped by Al-pairs in Ga/ZSM-5 at operation conditions. The findings are expected to pave the way for better understanding of the experimentally observed operation condition dependent PDH performance of Ga/ZSM-5.

Ga/ZSM-5 广泛用于催化丙烷脱氢（PDH）。在苛刻的操作条件下，Ga/ZSM-5 的详细活性物种以及导致观察到的卓越 PDH 性能的合理反应途径仍未得到解决。滞留在沸石框架 Al 对上的还原框架外 Ga 氢化物物种，包括 b[GaH]2+、[Ga]+-BAS、[GaH2]+-BAS 等，是一种重要的 Ga 物种，被称为 PDH 的活性物种。在这项工作中，我们在与实验相关的温度和压力下对这些镓物种的 PDH 途径进行了理论研究。我们发现，与其他氢化镓物种相比，动态生成的欠配位 b[GaH]2+ 在 PDH 条件下会表现出更高的催化活性。b[GaH]2+ 最合理的 PDH 途径是硒途径。Ga 物种和 BAS 在促进 H2 消解和 β-H 转移以及提高 PDH 效率方面发挥着协同作用。镓氢化物物种也可能作为中间体沿着 PDH 途径形成，作为随后活化和转化丙烷的活性位点，这表明在 Ga/ZSM-5 的操作条件下，镓氢化物物种被 Al 对所捕获。这些发现有望为更好地理解实验观察到的 Ga/ZSM-5 与操作条件有关的 PDH 性能铺平道路。

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引用次数: 0

In-situ generated hydrogen for selective hydrogenolysis of lignin catalyzed by Mg-Al mixed oxides with nested Ni nanoparticles 镁铝混合氧化物与嵌套镍纳米颗粒催化木质素选择性氢解产生的原位氢气

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2024-11-02 DOI: 10.1016/j.jcat.2024.115833

Yun Tian , Mengqiao Gao , Zhiyang Tang , Fukun Li , Qiang Zeng , Jinxing Long , Xuehui Li

Conversion of lignin to valuable chemicals without external hydrogen presents a significative but challengeable endeavor. Herein, an efficient approach has been proposed for the lignin hydrogenolysis with in-situ hydrogen in the presence of Ni nanoparticles nested in layered double oxides (LDOs). 84.4 % conversion of lignin was achieved over 30Ni-Mg₃Al-LDOs, affording a 21.3 % yield of monomers, and 38.0 % of which was identified as 4-ethylphenol. Catalyst characterizations revealed that this excellent performance of lignin conversion should be ascribed to the highly dispersed Ni nanoparticles, strong interfacial interactions between Ni and LDOs, and suitable basicity of catalysts. Furthermore, the roles of the solvent (1,4-dioxane aqueous solution) and the lignin methoxyl groups as hydrogen resources were distinguished, and the former acted as an initial hydrogen to promote lignin depolymerization, and the latter was responsible for the high yield of 4-ethylphenol. In addition, a plausible reaction pathway for lignin hydrogenolysis has been proposed.

在没有外部氢气的情况下将木质素转化为有价值的化学品是一项意义重大但极具挑战性的工作。本文提出了一种在层状双氧化物（LDOs）中嵌套镍纳米粒子的情况下利用原位氢气进行木质素氢解的有效方法。在 30Ni-Mg3Al-LDOs 上，木质素的转化率达到 84.4%，单体产率为 21.3%，其中 38.0%被鉴定为 4-乙基苯酚。催化剂特性分析表明，木质素转化的优异性能应归功于高度分散的镍纳米颗粒、镍与 LDOs 之间强烈的界面相互作用以及催化剂合适的碱性。此外，还区分了溶剂（1,4-二氧六环水溶液）和木质素甲氧基作为氢资源的作用，前者是促进木质素解聚的初始氢，后者是 4-乙基苯酚高产率的原因。此外，还提出了木质素氢解的合理反应途径。

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引用次数: 0

Lithium iodide promoted CO2 hydrogenation towards ethanol via biphasic lewis-acid-base pairs synergistic catalysis 碘化锂通过双相路易斯酸碱对协同催化促进二氧化碳加氢制乙醇

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2024-11-02 DOI: 10.1016/j.jcat.2024.115832

Ke Zheng , Yufeng Li , Huanhuan He, Bing Liu, Yuebing Xu, Xiaohao Liu

Ethanol synthesis via CO₂ hydrogenation is of great importance in view of its high-value utilization. Herein, combining with heterogeneous and homogenous catalysis, we have developed an efficient biphasic Lewis-acid-base pairs synergistic catalysis strategy from CO₂ hydrogenation. Apart from conventional heterogeneous ethanol synthesis route, it was surprisingly found that LiI homogenous promoter significantly enhanced CO₂ conversion, ethanol selectivity, and productivity. LiI promoted CO₂ dissolution in pure water and accelerated reaction intermediates consumption, favoring CO₂ conversion. In detail, it can weaken C-O bond of CH₃OH intermediate through Li⁺-I^- Lewis-acid-base catalysis. The formed CH₃I* with lower bond energy for C-I was more facile to dissociate into CH₃*, favoring its subsequent coupling with CO* to form ethanol. In combination of Rh₁/CeTiO_x catalyst, LiI promoter, and methanol as solvent, a record-breaking ethanol yield was achieved (223.1 mmol·g⁻¹·h⁻¹). The obtained ethanol yield was about 18.7 times of that reported the best result in literatures. Especially, the established catalyst system could also be applied for synthesis of higher-carbon-number alcohols by the CO₂ hydrogenation with other alcohols solvent (C_nH_2n+1OH, n = 2,3…).

二氧化碳加氢合成乙醇具有重要的高值化利用价值。在此，我们结合异相催化和均相催化，开发了一种高效的二氧化碳加氢双相路易斯酸碱对协同催化策略。除了传统的异相乙醇合成路线外，我们还惊喜地发现 LiI 均相促进剂能显著提高二氧化碳转化率、乙醇选择性和生产率。LiI 能促进二氧化碳在纯水中的溶解，加速反应中间产物的消耗，有利于二氧化碳的转化。具体而言，它能通过 Li+-I- 路易斯酸碱催化作用削弱 CH3OH 中间体的 C-O 键。形成的 CH3I* 与 C-I 的键能较低，更容易解离成 CH3*，有利于其随后与 CO* 偶联生成乙醇。结合使用 Rh1/CeTiOx 催化剂、LiI 促进剂和甲醇作为溶剂，乙醇产量达到了破纪录的水平（223.1 mmol-g-1-h-1）。所获得的乙醇产量约为文献报道最佳结果的 18.7 倍。特别是，所建立的催化剂体系还可应用于以其他醇类溶剂（CnH2n+1OH，n = 2、3......）进行 CO2 加氢合成更高碳数的醇类。

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引用次数: 0

Construction of magnetically separable S-scheme BiFeO3/Cl-g-C3N4 heterostructure photocatalyst for simultaneous removal of Cr(Ⅵ) and tetracycline in aqueous solution: Performance and mechanism insight 构建磁性可分离的 S 型 BiFeO3/Cl-g-C3N4 异质结构光催化剂，用于同时去除水溶液中的铬（Ⅵ）和四环素：性能和机理分析

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2024-10-28 DOI: 10.1016/j.jcat.2024.115821

Tianrui Xu , Guanghui Wang , Zehua Liu , Nansheng Deng , Xuewen Zhang

A green, efficient and recyclable magnetic BiFeO₃/Cl-g-C₃N₄ photocatalyst was prepared for the simultaneous removal of Cr(Ⅵ) and tetracycline (TC) from water by wet chemical and thermal synthesis methods. Experimental results revealed that BiFeO₃/Cl-g-C₃N₄ achieved a removal efficiency of 96.1 % for Cr(Ⅵ) and 98.2 % for TC under visible light irradiation for 50 min at pH 6. The results of the work function, charge density difference, UV–vis DRS, PL, PC and EIS tests indicate the formation of S-scheme heterojunctions between BiFeO₃ and Cl-g-C₃N₄, which exhibits superior carrier separation and migration efficiency. The evidence for interfacial charge transfer from BiFeO₃ to Cl-g-C₃N₄ within BiFeO₃/Cl-g-C₃N₄ was further corroborated by means of ISIXPS, EPR and KPFM. Moreover, calculations of the density of states demonstrate that the introduction of Cl enhances the reduction capability of BiFeO₃/Cl-g-C₃N₄. Results from ESR tests and trapping experiments has demonstrated that the singlet oxygen (¹O₂) and electrons are the primary active species. Furthermore, the high removal rates of TC and Cr(VI) from industrial wastewater and groundwater, coupled with the lower ecotoxicity of TC degradation intermediates, indicate that BiFeO₃/Cl-g-C₃N₄ has the potential for practical applications. After five cycles, the BiFeO₃/Cl-g-C₃N₄ still removed 90.5 % of TC and 96 % of Cr(Ⅵ).

制备了一种绿色、高效、可回收的磁性BiFeO3/Cl-g-C3N4光催化剂，用于同时去除镉（Ⅵ）和四环素（TC）。

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引用次数: 0

On the catalytic behaviors of Cu/SiO2 and Cu/γ-Al2O3 for dimethyl oxalate hydrogenation from microkinetic analysis including a plug flow reactor model 从塞流反应器模型的微动力学分析看 Cu/SiO2 和 Cu/γ-Al2O3 对草酸二甲酯加氢的催化行为

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2024-10-28 DOI: 10.1016/j.jcat.2024.115822

Han-Jie Xiao , Hui-Han Zheng , Ming Lei , Jing-Hong Zhou , De Chen , Xing-Gui Zhou , Yi-An Zhu

Cu-based catalysts have been widely used in dimethyl oxalate (DMO) hydrogenation due to their ability to activate C-O/C=O bonds without breaking C–C bonds. In this work, the electronic structures of Cu/SiO₂ and Cu/γ-Al₂O₃ as well as their catalytic performance have been studied by the machine-learning-based stochastic surface walking-global neural network potential (SSW-NN) method, density functional theory calculation, and microkinetic analysis including a plug flow reactor (PFR) model. Among SiO₂- and γ-Al₂O₃-supported Cu_n (n = 1–9), the Cu₅ and Cu₇ clusters are held most tightly on SiO₂(111) and γ-Al₂O₃(110), respectively. The electron transfer from Cu₅ to SiO₂(111) leads to the formation of Cu^δ+ and Cu⁰, which are responsible for the stabilization of unsaturated C and O atoms in the intermediates, respectively, while on γ-Al₂O₃(110) an electron-rich Cu⁰-Al_3c site is most active. Both the Cu^δ+-Cu⁰ and the Cu⁰-Al_3c sites synergistically catalyze the dissociation of gas-phase species and hydrogenation of intermediates. Under the typical operating conditions, although the selectivity towards methyl glycolate (MG) is invariably highest at the reactor inlet, Cu₅/SiO₂(111) and Cu₇/γ-Al₂O₃(110) are actually selective for the production of ethylene glycol (EG) and ethanol (EtOH), respectively, if the overall selectivity is taken into consideration, signifying the importance of including a reactor model to probe the kinetics of series of consecutive reactions. The dissociation of DMO is found to be the rate-determining step, and the high energy barrier for EG dissociation on Cu₅/SiO₂(111) hinders its deep hydrogenation while the relatively low barrier on Cu₇/γ-Al₂O₃(110) is beneficial to the formation of EtOH.

铜基催化剂具有活化 C-O/C = O 键而不破坏 C-C 键的能力，因此被广泛应用于草酸二甲酯（DMO）加氢反应。在这项工作中，通过基于机器学习的随机表面行走-全局神经网络势（SSW-NN）方法、密度泛函理论计算和微动力学分析（包括塞流反应器（PFR）模型），研究了 Cu/SiO2 和 Cu/γ-Al2O3 的电子结构及其催化性能。在 SiO2- 和 γ-Al2O3 支持的 Cun（n = 1-9）中，Cu5 和 Cu7 团簇分别在 SiO2(111) 和 γ-Al2O3(110) 上被最紧密地保持。从 Cu5 到 SiO2(111)的电子转移导致 Cuδ+ 和 Cu0 的形成，它们分别负责稳定中间产物中的不饱和 C 原子和 O 原子，而在γ-Al2O3(110)上，电子丰富的 Cu0-Al3c 位点最为活跃。Cuδ+-Cu0 和 Cu0-Al3c 两个位点协同催化气相物种的解离和中间产物的氢化。在典型的操作条件下，虽然反应器入口处对乙醇酸甲酯（MG）的选择性总是最高的，但如果考虑到整体选择性，Cu5/SiO2(111) 和 Cu7/γ-Al2O3(110) 实际上分别对乙二醇（EG）和乙醇（EtOH）的生产具有选择性，这表明包括反应器模型在内的一系列连续反应动力学探究的重要性。研究发现，DMO 的解离是决定速率的步骤，Cu5/SiO2(111) 上 EG 解离的高能垒阻碍了其深度氢化，而 Cu7/γ-Al2O3(110) 上相对较低的能垒则有利于 EtOH 的生成。

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引用次数: 0