Molecular Catalysis最新文献_第2页

Mechanistic insights into photocatalytic hydrogen evolution from crude glycerol solution over gold-decorated TiO2 nanostructures 从粗甘油溶液在金修饰TiO2纳米结构上光催化析氢的机理

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-12-10 DOI: 10.1016/j.mcat.2025.115657

Thanapol Sutthiphong , Auttawit Thoumrungroj , Pimchanok Longchin , Mali Hunsom

A series of gold-decorated titanium dioxide (Au_x/HT) photocatalysts was synthesized by a sequential hydrothermal and photodeposition for the photocatalytic reforming of glycerol solution to green hydrogen (H₂). The presence of metallic Au in the range of 0.25 to 1.50 wt. % had an insignificant effect on the TiO₂ crystallite size, phase composition, porosity, and bandgap values compared to the pristine HT. However, the Au decoration significantly enhanced the visible light response, suppressed the charge recombination, and promoted the charge carrier migration. Among all explored photocatalysts, the Au_0.75/HT exhibited the highest photocatalytic H₂ production, attributing to its high BET surface area and optimal hemispherical surface structure. Apart the glycerol concentration and photocatalyst loading, types of glycerol feedstocks had a significant impact on the H₂ production. Among all the evaluated glycerol types, the refined crude glycerol achieved the highest H₂ output at 15 vol. % glycerol concentration and a photocatalyst loading of 3.0 g/L. This resulted in an H₂ production rate of 216.2 µmol/g·h (or 387.6 µmol after 3 h), approximately 1.22 and 1.59 times higher than those from commercial- and crude glycerol, respectively. Additionally, it demonstrated an outstanding long-term H₂ production and cost-effectiveness ($8.3 /mmol), which was comparable to that of commercial glycerol and approximately 3.41 times cheaper than that of crude glycerol.

采用水热法和光沉积法制备了一系列镀金二氧化钛（Aux/HT）光催化剂，用于甘油溶液光催化重整制绿氢（H2）。与原始HT相比，0.25 ~ 1.50 wt. %的Au对TiO2晶粒尺寸、相组成、孔隙率和带隙值的影响不显著。而Au修饰明显增强了可见光响应，抑制了电荷复合，促进了载流子迁移。在所有的光催化剂中，由于Au0.75/HT具有较高的BET表面积和最佳的半球形表面结构，其光催化H2产率最高。除甘油浓度和光催化剂负载外，甘油原料类型对H2产率有显著影响。在所有被评价的甘油类型中，精制粗甘油在15 vol. %甘油浓度和光催化剂负载3.0 g/L时H2产量最高。结果表明，产氢率为216.2µmol/g·h (3 h后为387.6µmol)，分别是商品甘油和粗甘油产氢率的1.22和1.59倍。此外，它还具有出色的长期氢气产量和成本效益（8.3美元/mmol），与商业甘油相当，比粗甘油便宜约3.41倍。

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引用次数: 0

Bifunctional zinc porphyrin-based organic polymers with peripheral flexible linkers as efficient catalysts for CO2 cycloaddition reactions 具有外围柔性连接剂的双功能卟啉锌基有机聚合物作为CO2环加成反应的高效催化剂

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-12-10 DOI: 10.1016/j.mcat.2025.115655

Zhenping Su , Min Liu , Dongping Wang , Shengming Lu , Jun Li

Nowadays, bifunctional catalysts have attracted considerable attention for their superior catalytic efficiency in the cycloaddition reactions of CO₂ to produce corresponding cyclic carbonates. Herein, three bifunctional zinc porphyrin-based organic polymers Poly(ZnTAEImP/BDDA), Poly(ZnTAEImP/PPA) and Poly(ZnTAEImP/PD) were synthesized successfully through the free-radical copolymerization of a novel bifunctional zinc porphyrin ZnTAEImP with three structurally similar flexible linker monomers, 1,4-butanediol diacrylate (BDDA), phenyl ethylene glycol diacrylate (PPA), and 1,4-phenylene diacrylate (PD), respectively. A comprehensive series of characterizations were subsequently performed to verify the structural integrity and properties of the prepared polymers. All three polymers possessed well-defined bifunctional active sites, including Zn²⁺ Lewis acid centers and Br⁻ nucleophilic species. Among them, the Poly(ZnTAEImP/PD) demonstrated exceptional solvent-responsive swelling capacity and robust thermal stability. Notably, Poly(ZnTAEImP/PD) exhibited superior catalytic performance in the cycloaddition reaction between CO₂ and epichlorohydrin (ECH), achieving 99% cyclic carbonate yield under optimized conditions (1.0 MPa CO₂, 120 °C, 12 h). Additionally, Poly(ZnTAEImP/PD) also displayed broad substrate universality and excellent cycling stability, indicating promising application prospects.

目前，双功能催化剂因其在CO2的环加成反应中具有优异的催化效率而备受关注。本文通过一种新型双功能卟啉锌ZnTAEImP与三种结构相似的柔性连接单体1,4-丁二醇二丙烯酸酯（BDDA）、苯基乙二醇二丙烯酸酯（PPA）和1,4-苯基二丙烯酸酯（PD）自由基共聚，成功合成了三种双功能卟啉锌基有机聚合物Poly（ZnTAEImP/BDDA）、Poly（ZnTAEImP/PPA）和Poly（ZnTAEImP/PD）。随后进行了一系列全面的表征，以验证所制备聚合物的结构完整性和性能。这三种聚合物都具有明确的双功能活性位点，包括Zn 2 +路易斯酸中心和Br亲核物质。其中，聚（ZnTAEImP/PD）表现出优异的溶剂响应膨胀能力和强大的热稳定性。值得注意的是，Poly（ZnTAEImP/PD）在CO₂与环氧氯丙烷（ECH）的环加成反应中表现出优异的催化性能，在优化条件（1.0 MPa CO₂，120°C, 12 h）下可达到99%的环碳酸盐收率。此外，Poly（ZnTAEImP/PD）还表现出广泛的衬底通用性和良好的循环稳定性，具有广阔的应用前景。

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引用次数: 0

Fabrication of 1D/2D WO3 nanorods@Ti3C2Tx Schottky junctions for photocatalytic removal of the insecticide Clothianidin from aqueous matrices 制备一维/二维WO3 nanorods@Ti3C2Tx Schottky结光催化脱除水中的杀虫剂噻虫胺

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-12-09 DOI: 10.1016/j.mcat.2025.115656

Christos Lykos , Charalampos Drivas , Mark A. Isaacs , Kalliopi Ladomenou , George Z. Kyzas , Triantafyllos Albanis , Ioannis Konstantinou

Tungsten trioxide (WO₃) is an n-type semiconductor with a relatively narrow band gap, which enables its photoactivation under visible light. However, its application in various photocatalytic processes is constrained by the rapid recombination of photogenerated charge carriers. In this study, 1D/2D Schottky junctions were fabricated to mitigate the recombination phenomenon by combining WO₃ nanorods (WRs) with small quantities of Ti₃C₂T_x MXene. The morphological, structural, and optical properties of the composite materials were examined using various characterization techniques. Furthermore, their photocatalytic performance under simulated solar light was assessed by monitoring the degradation of the insecticide Clothianidin, which served as a model emerging contaminant. The results indicated that the incorporation of 5% ^W/_W Ti₃C₂T_x with WRs significantly enhances photocatalytic efficiency by approximately 50%. This improvement was attributed to the migration of photogenerated electrons to the Fermi level (E_f) of the MXene, leading to the formation of a Schottky barrier at the interface between the two materials, which impedes electron backflow. Therefore, recombination between positive holes and photogenerated electrons was effectively suppressed, as evidenced by photoluminescence spectroscopy. Scavenging experiments demonstrated that hydroxyl radicals are the primary reactive species involved in the degradation of Clothianidin, with positive holes contributing to a lesser extent. Overall, the findings of this study highlight the potential of MXenes, such as Ti₃C₂Tx, to enhance the photocatalytic efficiency of WO₃ nanorods via the formation of Schottky junctions. This advancement promotes the application of these photocatalytic materials in large-scale processes associated with wastewater remediation and green fuel production.

三氧化钨（WO₃）是一种带隙相对较窄的n型半导体，这使得它在可见光下能够被光激活。然而，它在各种光催化过程中的应用受到光生成载流子快速重组的限制。在这项研究中，通过将WO₃纳米棒（ws）与少量的Ti3C2Tx MXene结合，制备了1D/2D Schottky结来减轻重组现象。使用各种表征技术检测了复合材料的形态、结构和光学性质。此外，通过监测杀虫剂噻虫胺（Clothianidin）作为新型污染物的降解情况，评估了它们在模拟太阳光照下的光催化性能。结果表明，WRs中掺入5% W/W的Ti3C2Tx可显著提高WRs光催化效率约50%。这种改进归因于光电子迁移到MXene的费米能级（Ef），导致在两种材料之间的界面形成肖特基势垒，从而阻碍了电子回流。因此，正如光致发光光谱所证明的那样，正空穴和光生电子之间的复合被有效抑制。清除实验表明，羟基自由基是参与Clothianidin降解的主要活性物质，而正空穴的作用较小。总的来说，这项研究的发现突出了MXenes的潜力，比如Ti₃C₂Tx，通过形成肖特基结来提高WO₃纳米棒的光催化效率。这一进展促进了这些光催化材料在废水修复和绿色燃料生产等大规模工艺中的应用。

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引用次数: 0

Facilitated aerobic oxidation of lignin model alcohols over microwave-synthesized vanadium carbide core-shell catalysts with oxovanadium active shell 微波合成氧化钒核壳催化剂促进木质素模型醇的有氧氧化

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-12-09 DOI: 10.1016/j.mcat.2025.115633

M.O. Lukashov , E.A. Eseva , V.D. Elsesser , D.D. Davtyan , A.M. Aghoyan , K.A. Cherednichenko , Y.V. Timchenko , I.A. Rodin , A.V. Akopyan

The development of catalysts for the selective oxidation of biomass-based alcohols in order to increase valorization of lignin is an urgent task in the transition to renewable sources of hydrocarbons. In this work, catalysts based on VC with a core-shell structure have been obtained by microwave irradiation. This synthesis method makes it possible to produce carbide catalysts using inexpensive equipment in an extremely short time (15 min). The VC_m.b. catalyst exhibits remarkable activity in the aerobic oxidation reaction of benzyl alcohol with 100 % aldehyde selectivity. It was found that VC catalyst contains the surface oxovanadium species in various states, a large number of oxygen vacancies acts as Lewis’s acid sites, and has high acidic properties that promote effective oxidation of aromatic alcohols. The VC_m.b. catalyst demonstrates a 5–7-fold increase in oxidation rate compared to analogues based on noble metals, as well as the possibility of recycling for at least 5 cycles. It is shown that the VC_m.b. catalyst can effectively oxidize benzyl alcohol to benzaldehyde using air under optimal conditions: 140 °C, 1 h, 8 atm, 4.3 mg/mL VC_m.b., 0.5 wt.% substrate. It is noted that surface oxovanadium sites are capable of strongly chemisorbing particles whose atoms are electron pair donors, including methoxy substituted aromatic alcohols, leading to the effect of irreversible adsorption. Mechanism studies reveal that the aerobic oxidation of benzyl alcohol into the corresponding aldehyde can proceed using chemosorbed oxygen on the catalyst surface, and atmospheric oxygen is activated to form the superoxide radical O₂^•- and singlet oxygen ¹O₂.

在向可再生碳氢化合物过渡的过程中，开发生物质醇选择性氧化催化剂以提高木质素的增值是一项紧迫的任务。本文采用微波辐照法制备了具有核壳结构的VC催化剂。这种合成方法使得在极短的时间内（15分钟）使用廉价的设备生产碳化物催化剂成为可能。VCm.b。该催化剂在苯甲醇的有氧氧化反应中表现出良好的活性，醛选择性为100%。研究发现VC催化剂表面含有多种状态的氧钒，大量的氧空位作为Lewis酸位，具有高酸性，促进芳香醇的有效氧化。VCm.b。与基于贵金属的类似物相比，催化剂的氧化速率提高了5 - 7倍，并且可以循环使用至少5次。结果表明，VCm.b。催化剂在140℃、1 h、8 atm、4.3 mg/mL VCm.b的最佳条件下，能有效地将苯甲醇氧化为苯甲醛。， 0.5 wt.%底物。研究发现，表面氧化钒位点能够对具有电子对供体的粒子（包括甲氧基取代芳香醇）进行强化学吸附，从而产生不可逆吸附效果。机理研究表明，苯甲醇的好氧氧化生成相应的醛可以利用催化剂表面的化学吸附氧进行，大气中的氧被活化形成超氧自由基O2•-和单线态氧1O2。

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引用次数: 0

Enhanced catalytic performance of palladium supported on graphitic carbon nitride for acetylene hydrochlorination 氮化石墨碳负载钯对乙炔加氢氯化反应的增强催化性能

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-12-08 DOI: 10.1016/j.mcat.2025.115642

Zeyu Liu , Lu Wang , Haijun Yan , Shahid Ali , Chao Yang , Ronglan Wu , Jide Wang , Yana Wei , Hui Sun , Changhai Liang

In response to the stringent mercury restrictions of the Minamata Convention, replacing mercury-based catalysts with precious metal alternatives for polyvinyl chloride (PVC) production has become imperative. However, the deactivation of Pd-based catalysts poses a significant challenge for acetylene hydrochlorination. Herein, a graphitic carbon nitride (g-C₃N₄)-modified activated carbon (AC) support to stabilize Pd catalysts was reported and the optimized Pd-g-C₃N₄/AC catalyst exhibited exceptional activity, achieving 95 % acetylene conversion and 99 % vinyl chloride selectivity for over 10 h. Combined characterization and density functional theory (DFT) simulations revealed that the g-C₃N₄ incorporation modulates the microelectronic environment of Pd active sites, thereby balancing the adsorption energy difference between acetylene and hydrogen chloride on the catalyst surface. This balance enables the reactants to participate in the reaction in a timely manner, which is identified as the fundamental mechanism behind the improved catalytic stability. This work offers a design strategy for high-performance, mercury-free Pd-based catalysts for acetylene hydrochlorination.

为响应《水俣公约》对汞的严格限制，用贵金属替代品取代汞基催化剂用于聚氯乙烯（PVC）生产已势在必行。然而，钯基催化剂的失活对乙炔加氢氯化反应提出了重大挑战。本文报道了一种石墨碳氮（g-C3N4）修饰的活性炭载体（AC）来稳定钯催化剂，优化后的Pd-g-C3N4/AC催化剂表现出优异的活性，在超过10小时的时间内实现了95%的乙炔转化率和99%的氯乙烯选择性。结合表征和密度功能理论（DFT）模拟表明，g-C3N4的加入调节了钯活性位点的微电子环境。从而平衡了乙炔和氯化氢在催化剂表面的吸附能差。这种平衡使反应物能够及时参与反应，这被认为是提高催化稳定性的基本机制。这项工作为乙炔加氢氯化反应提供了一种高性能、无汞钯基催化剂的设计策略。

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引用次数: 0

Surface functionalization of Fe/g-C3N4 for highly selective formation of light olefins in Fischer-Tropsch synthesis 费托合成中Fe/g-C3N4高选择性形成轻烯烃的表面功能化

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-12-07 DOI: 10.1016/j.mcat.2025.115653

Shuai Zhang , Xuejian Zhang , Ke Li , Kangzhou Wang , Caihu Li , Xinhua Gao , Qingxiang Ma , Tian-Sheng Zhao , Jianli Zhang

Fischer-Tropsch synthesis (FTS) is a key process for the catalytic conversion of carbon containing resources into liquid fuels and high-value chemicals. Regulating product distribution to achieve highly selective olefin production via FTS over Fe-based catalysts is of great research significance. In this study, a surface oxidation strategy was adopted to achieve surface functionalization of Fe/g-C₃N₄, and the regulatory mechanisms of surface groups introduced by different oxidants on the textural properties, surface characteristics, reduction and adsorption behaviors, as well as the catalytic performance of Fe/g-C₃N₄ in CO hydrogenation were systematically investigated. The results indicate that HNO₃ treatment can promote the conversion of pyridinic N to pyrrolic N ing-C₃N₄, and enhance the reducibility and carburization of iron species. In CO hydrogenation, the Fe/g-C₃N₄-HNO₃ catalyst exhibits a high olefin/paraffin ratio (O/P=4.91) and C_2–4⁼ selectivity (49.54%) in the absence of any alkali metal modification. The strong electronic effect of pyrrolic N significantly enhanced the olefin selectivity and chain propagation of the Fe-based catalyst in FTS.

费托合成（FTS）是含碳资源催化转化为液体燃料和高价值化学品的关键过程。在铁基催化剂上调控产物分布，实现高选择性烯烃生产具有重要的研究意义。本研究采用表面氧化策略实现Fe/g-C3N4的表面功能化，系统研究了不同氧化剂引入的表面基团对Fe/g-C3N4的结构性质、表面特征、还原吸附行为以及CO加氢催化性能的调控机制。结果表明，HNO3处理能促进吡啶N向吡啶N - c3n4的转化，提高铁种的还原性和渗碳能力。在CO加氢过程中，Fe/g-C3N4-HNO3催化剂在没有任何碱金属修饰的情况下，具有较高的烯烃/石蜡比（O/P=4.91）和选择性（49.54%）。吡咯N的强电子效应显著提高了ft中fe基催化剂的烯烃选择性和链扩展。

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引用次数: 0

Polyurethane-based heterogeneous catalysts with highly dispersed Rh single sites for reductive hydroformylation of olefins 具有高度分散Rh单位点的聚氨酯基非均相催化剂用于烯烃的还原性氢甲酰化反应

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-12-06 DOI: 10.1016/j.mcat.2025.115654

Maria V. Nenasheva , Bogdan O. Protsenko , Kirill D. Kulaev , Evgeny R. Naranov , Alexander L. Trigub , Anton L. Maximov , Alexander A. Guda , Dmitry N. Gorbunov

The design of novel active and stable heterogeneous catalysts for industrially important hydroformylation reaction is a challenging task. In our study, we report the first non-phosphoric polyurethane-based hydroformylation catalyst, which is also active in hydrogenation of aldehydes under hydroformylation conditions for one-step transformation of olefins to primary alcohols. The catalyst was found to be active in the reductive hydroformylation of the model substrate (1-hexene), as well as a range of other unsaturated substrates. At longer reaction times, alcohols were the dominant products. Also, the catalyst showed a sufficient reusability. We prove that Rh atoms in the catalyst are present in the form of highly coordinated complexes both before and after reductive hydroformylation. Based on the in situ Rh K-edge X-ray absorption spectroscopy we propose the structure of Rh active sites.

为工业上重要的氢甲酰化反应设计新型活性稳定的多相催化剂是一项具有挑战性的任务。在我们的研究中，我们报道了第一个基于非磷聚氨酯的氢甲酰化催化剂，该催化剂在氢甲酰化条件下对烯烃一步转化为伯醇的醛的加氢反应中也很活跃。该催化剂在模型底物（1-己烯）以及一系列其他不饱和底物的还原性氢甲酰化反应中具有活性。在较长的反应时间内，醇是主要产物。该催化剂具有良好的可重复使用性。我们证明了催化剂中的Rh原子在还原氢甲酰化前后都以高度配位配合物的形式存在。基于原位Rh k边x射线吸收光谱，我们提出了Rh活性位点的结构。

引用次数: 0

Exploring the potential reactivity of binuclear Pd active sites in NO direct decomposition on Pd/SSZ-13: A DFT study Pd/SSZ-13上NO直接分解中双核Pd活性位点的潜在反应性探讨：DFT研究

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-12-05 DOI: 10.1016/j.mcat.2025.115650

Lu Wang, Yongheng Li, He Chen, Xingyong Wang, Hongchen Li, Ruoqian Zhang, Songbao Fu

This study utilized DFT methods to examine whether binuclear Pd sites confined in SSZ-13 could provide a feasible pathway for the direct decomposition of NO. Based on previous observations suggesting that SSZ-13 with a Si/Al ratio of 10:1 provides a representative coordination environment, a corresponding structural model was constructed. Bridge configurations of Pd(0), Pd(I), and Pd(II) located within either eight-membered or six-membered rings were then evaluated. Model screening and mechanistic analysis revealed that binuclear Pd bridges in eight-membered rings are significantly more stable, whereas those in six-membered rings tend to break apart. The intrinsic mechanistic behaviors of Pd species with different oxidation states were analyzed in detail, with particular emphasis on how variations in electron-donating capability influence NO adsorption, ONNO formation, NO bond cleavage, and subsequent steps of the reaction cycle. Among the examined configurations, Pd(I) exhibits the most favorable intrinsic energetics for the elementary steps of NO decomposition. Kinetic analysis based on TST further confirmed the intrinsic trend Pd(I) > Pd(0) > Pd(II), consistent with qualitative observations of pseudo-metallic Pd species in previous experimental studies. Meanwhile, N₂O formation and oxygen accumulation were identified as key factors that could promote oxidative deactivation. These theoretical insights will provide predictive guidance for future experimental investigations into the reactivity of Pd sites in SSZ-13.

本研究利用离散傅里叶变换（DFT）方法考察了SSZ-13中的双核Pd位点是否可以为NO的直接分解提供可行的途径。基于前人的观察，Si/Al比为10:1的SSZ-13提供了一个具有代表性的配位环境，我们构建了相应的结构模型。然后评估了位于八元环或六元环内的Pd(0)、Pd(I)和Pd（II）的桥构型。模型筛选和机制分析表明，八元环中的双核Pd桥明显更稳定，而六元环中的双核Pd桥则倾向于断裂。详细分析了不同氧化态Pd的内在机理行为，重点研究了供电子能力的变化如何影响NO吸附、ONNO形成、NO键裂解以及反应周期的后续步骤。在所研究的构型中，Pd(I)在NO分解的基本步骤中表现出最有利的内在能量学。基于TST的动力学分析进一步证实了Pd(I) > Pd(0) > Pd（II）的内在趋势，与以往实验研究中对伪金属钯的定性观察结果一致。同时，N2O的形成和氧的积累是促进氧化失活的关键因素。这些理论见解将为未来对SSZ-13中Pd位点反应性的实验研究提供预测指导。

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引用次数: 0

Electrocatalytic hydrogenation of cinnamaldehyde over Pd catalysts regulated by cosolvent electrolyte 助溶剂电解质调控Pd催化剂上肉桂醛的电催化加氢反应

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-12-05 DOI: 10.1016/j.mcat.2025.115649

Jie Xie , Qunwu Huang , Jinli Zhang , Yan Fu

Rational control of the product selectivity for α, β-unsaturated aldehyde hydrogenation is still a challenging task now. Herein, a 3D porous Pd electrode with dendrite-like morphology was fabricated through a facile one-step potentiostatic electrodeposition in a K₂PdCl₆ electroplating solution. The Pd-x catalyst series via simply controlling the deposition time, were employed for the electrocatalytic hydrogenation (ECH) of cinnamaldehyde (CAL) in different cosolvent electrolytes. Intriguingly, over the same Pd catalyst, ECH of CAL exhibits outstanding selectivity toward C=O bond in the water-acetonitrile system at relatively low potential, whereas it shows high selectivity toward C=C bond in the water–methanol system at relatively high potential. Hydrogen scavenging and kinetics experiments demonstrate that ECH of CAL is predominantly governed via proton coupled electron transfer based on the Eley–Rideal mechanism. In-situ electrochemical spectroscopy reveals that the C=O bond of CAL is preferentially activated on the Pd surface in the water-acetonitrile system, while a distinct adsorption mode of CAL is observed in the water–methanol system. The potential-driven evolution of interfacial water structure is greatly associated with the proton transfer process and thereby affects the ECH efficiency. This work presents a new approach for controlling selectivity in electrocatalytic reactions relying on cosolvent effects along with electrode potential.

合理控制α， β-不饱和醛加氢反应的产物选择性仍然是一个具有挑战性的课题。本文在K2PdCl6电镀液中，通过简单的一步恒电位电沉积法制备了具有枝晶状形貌的三维多孔Pd电极。通过简单控制沉积时间，Pd-x系列催化剂在不同的助溶剂电解质中进行了肉桂醛（CAL）的电催化加氢（ECH）。有趣的是，在相同的Pd催化剂上，CAL的ECH在相对低电位的水-乙腈体系中对C=O键表现出突出的选择性，而在相对高电位的水-甲醇体系中对C=C键表现出较高的选择性。氢清除实验和动力学实验表明，CAL的ECH主要是由基于eley - ideal机制的质子耦合电子转移控制的。原位电化学光谱分析表明，在水-乙腈体系中，CAL的C=O键优先在Pd表面被激活，而在水-甲醇体系中，CAL有明显的吸附模式。电位驱动的界面水结构演变与质子转移过程密切相关，从而影响ECH效率。这项工作提出了一种依靠共溶剂效应和电极电位控制电催化反应选择性的新方法。

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引用次数: 0

The role of zeolite type in Ru/zeolite catalysts for ammonia decomposition to hydrogen 沸石类型在Ru/沸石催化剂氨分解制氢中的作用

IF 4.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-12-05 DOI: 10.1016/j.mcat.2025.115624

Shaofeng Gong , Yongming Mao , Zhenrong Hu , Zexue Du

Ammonia (NH₃) decomposition is a carbon-neutral pathway for hydrogen (H₂) production, with efficient catalysts being essential. Ruthenium (Ru)-based catalysts exhibit high activity, with support choice critically influencing performance. In this study, five commercial zeolites (NaY, NaX, NaZSM-5, Naβ, and NaSSZ-13) were used to synthesize Ru/zeolite catalysts by impregnation, and the catalytic performance of these catalysts was systematically evaluated. Among all catalysts tested, 1Ru/Naβ demonstrated the highest activity. At 500 °C (GHSV = 9000 mLNH₃·g_cat^-1·h^-1), it achieved a H₂ formation rate of 858 mmol·g_Ru^-1·min^-1 with a turnover frequency of 11.6 s^-1. Furthermore, when the temperature was raised to 550 °C, it attained a 99.2 % NH₃ conversion. This superiority arises from Naβ's strong basicity (enhancing electron donation to Ru and facilitating N₂ desorption, the rate-determining step), strong metal-support interaction (modifying Ru’s electronic properties), and favorable pore structures (abundant mesopores and large micropores that facilitate mass transfer). Ru sintering was identified as the main deactivation mechanism. This work provides guidance for designing high-performance Ru-based catalysts by selecting optimal zeolite supports.

氨（NH3）分解是氢（H2）生产的碳中性途径，高效的催化剂是必不可少的。钌（Ru）基催化剂表现出高活性，载体选择对其性能有重要影响。本研究以5种商业沸石（NaY、NaX、NaZSM-5、Naβ和NaSSZ-13）为原料，通过浸渍法制备了Ru/沸石催化剂，并对催化剂的催化性能进行了系统评价。在所有测试的催化剂中，1Ru/Naβ表现出最高的活性。在500℃（GHSV = 9000 mLNH3·gcat-1·h-1）条件下，H2生成速率为858 mmol·gRu-1·min-1，转换频率为11.6 s-1。当温度提高到550℃时，NH3转化率达到99.2%。这种优势源于Naβ的强碱性（增强Ru的电子赋能并促进N2脱附，这是决定速率的步骤），强金属-载体相互作用（改变Ru的电子性质），以及有利的孔隙结构（丰富的介孔和有利于传质的大微孔）。钌烧结是主要的失活机理。本研究为优化沸石载体设计高性能钌基催化剂提供了指导。

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引用次数: 0