Applied Catalysis A: General最新文献_第6页

Limitations of proton-conducting materials as supports for Pt-catalyzed ethane dehydrogenation in membrane reactors 质子导电材料作为膜反应器中pt催化乙烷脱氢载体的局限性

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-12-14 DOI: 10.1016/j.apcata.2025.120749

Jord P. Haven, Leon Lefferts, Jimmy A. Faria Albanese

Olefin formation via non-oxidative dehydrogenation of light alkanes is limited by thermodynamic equilibrium. A possible strategy to increase olefin yields aims at removing H₂ from the reaction zone using ceramic proton-conducting membranes. An attractive proposition is to deposit the catalyst directly onto the proton-conducting material to optimize hydrogen transport. To test this concept a Pt dehydrogenation catalyst was deposited onto lanthanum tungstate (LWO) and barium zirconium cerium yttrium (BZCY) oxides, which are prototypical materials in proton-conducting ceramics. The performance of Pt/LWO and Pt/BZCY was compared to a conventional Pt/ZnAl₂O₄ dehydrogenation catalyst in the non-oxidative dehydrogenation of ethane. The ethylene selectivity on Pt/LWO and Pt/BZCY was much lower than for Pt/ZnAl₂O₄, at the cost of a higher methane selectivity. Methane formation is possibly boosted by C-C cleavage on Lewis acid sites of the LWO and BZCY supports. These acid sites originate from the presence of oxygen vacancies in LWO and BZCY. Additionally, Pt/LWO deactivated rapidly in dry atmospheres, due to Pt sintering. This sintering, however, was suppressed when cofeeding steam. The presence of steam, unfortunately, further decreased ethylene selectivity for Pt/LWO. The Pt/BZCY system was comparably stable relative to Pt/LWO, which was attributed to relatively strong interactions between Pt and the Ba in the support. Implementing proton-conducting materials, like LWO and BZCY, as catalyst supports requires significant improvements to compete with the conventional Pt/ZnAl₂O₄ catalyst. Addressing this issue will be key to enable large-scale implementation of proton ceramic catalytic membrane reactors for alkane dehydrogenation.

轻烷烃非氧化脱氢生成烯烃受到热力学平衡的限制。提高烯烃产量的一个可能的策略是利用陶瓷质子传导膜从反应区去除H2。一个有吸引力的建议是将催化剂直接沉积在质子导电材料上，以优化氢的传输。为了验证这一概念，将Pt脱氢催化剂沉积在钨酸镧（LWO）和钡锆铈钇（BZCY）氧化物上，这是质子导电陶瓷的原型材料。研究了Pt/LWO和Pt/BZCY在乙烷非氧化脱氢反应中的性能，并与常规Pt/ZnAl2O4脱氢催化剂进行了比较。Pt/LWO和Pt/BZCY的乙烯选择性比Pt/ZnAl2O4低得多，代价是甲烷选择性更高。甲烷的形成可能是由LWO和BZCY载体的Lewis酸位点上的C-C裂解促进的。这些酸位来源于LWO和BZCY中氧空位的存在。此外，由于Pt烧结，Pt/LWO在干燥气氛中迅速失活。然而，当共进蒸汽时，这种烧结被抑制。不幸的是，蒸汽的存在进一步降低了Pt/LWO的乙烯选择性。相对于Pt/LWO， Pt/BZCY体系相对稳定，这是由于Pt与支架中Ba之间的相互作用相对较强。实现质子导电材料，如LWO和BZCY，作为催化剂支撑需要显著改进，以与传统的Pt/ZnAl2O4催化剂竞争。解决这一问题将是大规模实施质子陶瓷催化膜反应器进行烷烃脱氢的关键。

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引用次数: 0

Bis(phenylsulfonyl)imide-functionalized fiber: A high-performance catalyst for the synthesis of benzimidazole and bisindole derivatives 双（苯基磺酰）亚胺功能化纤维：合成苯并咪唑和双吲哚衍生物的高性能催化剂

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-12-13 DOI: 10.1016/j.apcata.2025.120747

Junxiang Li , Guanyu Zhou , Chang Li , Jian Xiao , Lu Wang

A bis(benzenesulfonyl)imide-functionalized fiber (PAN_BBI-1F) was successfully fabricated via a simple two-step chemical bonding approach and applied in acid-catalyzed organic synthesis. The physical and chemical structures of PAN_BBI-1F were precisely analyzed by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), while its excellent thermal stability within the temperature range of 30–300 °C was confirmed through thermogravimetric analysis (TGA). The optimal catalytic conditions for PAN_BBI-1F were investigated through cyclocondensation reactions between o-phenylenediamine and β-ketoesters. Additionally, PAN_BBI-1F demonstrated versatility in the synthesis of benzimidazole and bisindole derivatives (40 examples), achieving satisfactory yields of 48–97 % for benzimidazoles and 48–93 % for bisindoles in ethanol or water as the solvent. Furthermore, PAN_BBI-1F maintained catalytic activity over 5 consecutive cycles in the synthesis of benzimidazoles, with yields gradually decreasing from 97 % to 91 %. Elemental analysis (EA) further indicated that the sulfur content of PAN_BBI-1F decreased only slightly from 4.40 % to 4.32 % after repeated use, confirming its excellent recyclability. Finally, a plausible heterogeneous acid catalytic mechanism was proposed based on the PAN_BBI-1F-catalyzed cyclocondensation reaction as a representative example.

采用简单的两步化学键法制备了双（苯磺酰）亚胺功能化纤维（PANBBI-1F），并将其应用于酸催化有机合成。利用傅里叶变换红外光谱（FTIR）、x射线衍射（XRD）、x射线光电子能谱（XPS）和扫描电镜（SEM）对PANBBI-1F的物理和化学结构进行了精确分析，并通过热重分析（TGA）证实了其在30-300℃温度范围内的优异热稳定性。通过邻苯二胺与β-酮酯的环缩合反应，研究了panbb - 1f的最佳催化条件。此外，panbi - 1f在苯并咪唑和双吲哚衍生物的合成中表现出多用途性（40个例子），在乙醇或水作为溶剂的情况下，苯并咪唑和双吲哚的产率分别达到48-97 %和48-93 %。此外，panbb - 1f在合成苯并咪唑的连续5个循环中保持催化活性，产率从97 %逐渐下降到91 %。元素分析（EA）进一步表明，重复使用后，panbb - 1f的硫含量仅从4.40 %略微下降到4.32 %，证实了其良好的可回收性。最后，以panbbi - 1f催化的环缩合反应为代表，提出了一种合理的多相酸催化机理。

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引用次数: 0

Synergistic B/N coordination engineering in graphene-based single-atom catalysts for efficient ORR/ OER/HER: A DFT study 石墨烯单原子催化剂的协同B/N配位工程：高效ORR/ OER/HER的DFT研究

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-12-11 DOI: 10.1016/j.apcata.2025.120745

Zeyu Wang , Lili Sun , Wolong Li , Yongcun Li , Yong Wang

The rational design and development of multifunctional catalysts remain a major challenge for next-generation energy conversion and storage devices. In this study, density functional theory (DFT) calculations were employed to investigate graphene-based single-atom catalysts. Four boron (B) atoms and two nitrogen (N) atoms were incorporated into the second coordination shell of monolayer graphene, substituting carbon atoms in the lattice. A systematic evaluation of 15 transition metals (TM=Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ir, Pt) anchored at active sites was performed to assess their structural stability and catalytic activity toward the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). The results demonstrate that modulation of the local coordination environment effectively tunes the electronic structure of transition-metal centers, thereby optimizing the adsorption behavior of key intermediates. Several promising configurations were identified that simultaneously enhance ORR, OER, and HER performance, among which Co@BN/G (0.35 V/0.47 V/0.09 V) and Rh@BN/G (0.28 V/0.25 V) exhibited particularly favorable activity and stability metrics. These findings underscore the potential of B/N coordination engineering for the development of high-performance, durable electrocatalysts. This work provides fundamental theoretical insights and practical design strategies for the advancement of multifunctional catalysts in rechargeable zinc air batteries.

多功能催化剂的合理设计和开发仍然是下一代能量转换和存储设备面临的主要挑战。本研究采用密度泛函理论（DFT）对石墨烯基单原子催化剂进行了研究。4个硼(B)原子和2个氮(N)原子被纳入单层石墨烯的第2配位壳层，取代晶格中的碳原子。系统评价了锚定在活性位点的15种过渡金属（TM=Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ru、Rh、Pd、Ir、Pt）的结构稳定性和对氧还原反应（ORR）、析氧反应（OER）和析氢反应（HER）的催化活性。结果表明，局部配位环境的调节可以有效地调节过渡金属中心的电子结构，从而优化关键中间体的吸附行为。确定了几种有希望同时提高ORR， OER和HER性能的配置，其中Co@BN/G（0.35 V/0.47 V/0.09 V）和Rh@BN/G（0.28 V/0.25 V）表现出特别有利的活性和稳定性指标。这些发现强调了B/N协同工程在开发高性能、耐用电催化剂方面的潜力。本研究为可充电锌空气电池中多功能催化剂的发展提供了理论基础和实践设计策略。

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引用次数: 0

Direct oxidative carbonylation of waste methane to acetic acid over Rh/zeolite catalysts 在Rh/沸石催化剂上，废甲烷直接氧化羰基化制乙酸

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-12-11 DOI: 10.1016/j.apcata.2025.120744

Jialin Yu , Olukayode Gideon Oloyede , Mark B.F. Berko , Kunlun Ding , Richard J. Lewis , Stuart H. Taylor , Graham J. Hutchings , Kang Li , David Chadwick

Direct oxidation of methane to oxygenates remains challenging in heterogeneous catalysis. In this work, direct oxidative carbonylation of low-concentration methane to acetic acid has been investigated over Rh/zeolite catalysts. Formation of acetic acid over Rh/ZSM-5 is shown to be far superior compared to a range of other Rh/zeolite catalysts, including Rh/Z-beta, Rh/Z-Y, Rh/Mor, Rh/Fer, and Rh/SSZ-13. The importance of the 3D channel structure of ZSM-5 is emphasised by a comparison with unidirectional Rh/ZSM-23 which showed much lower production of acetic acid. Acetic acid production is found to be maximum at a SiO₂/Al₂O₃ ratio corresponding to ZSM5–50. Isolated Rh is identified as the active site for liquid oxygenate production with 0.09 wt% Rh/ZSM5 giving the highest acetic acid production. Higher Rh loading leads to a drop in production due to the gradual formation of Rh nanoparticles. Acetic acid production is shown to be strongly pressure dependent consistent with 2nd or higher order apparent kinetics compared to apparent 1st order for C1 products. Competing direct CO oxidation to CO₂ was responsible for above 85 % of the total CO₂ production. These findings highlight the critical role of zeolite topology in enhancing selective methane valorisation over Rh catalysts, and provide insights into developing practical catalytic processes for low-carbon chemical manufacturing.

在非均相催化中，直接氧化甲烷生成含氧化合物仍然具有挑战性。本文研究了低浓度甲烷在Rh/沸石催化剂上直接氧化羰基化制乙酸的反应。在Rh/ZSM-5催化剂上生成乙酸的能力远远优于其他一系列Rh/沸石催化剂，包括Rh/z - β、Rh/Z-Y、Rh/Mor、Rh/Fer和Rh/SSZ-13。通过与单向Rh/ZSM-23的比较，强调了ZSM-5的3D通道结构的重要性，后者显示出更低的醋酸产量。当SiO2/Al2O3比值为ZSM5-50时，乙酸产量最大。分离的Rh被确定为生产液态氧的活性位点，0.09 wt% Rh/ZSM5的乙酸产量最高。由于Rh纳米颗粒的逐渐形成，较高的Rh负载导致产量下降。与C1产物的一级表观动力学相比，乙酸的生成与二级或更高一级表观动力学表现出强烈的压力依赖性。竞争直接CO氧化成CO2占总CO2产量的85% %以上。这些发现强调了沸石拓扑结构在提高Rh催化剂选择性甲烷增值方面的关键作用，并为开发低碳化学制造的实用催化工艺提供了见解。

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引用次数: 0

Tailoring silver nanostructures for enhanced CO2 reduction: Insights from In-situ SERS and electrochemical studies 裁剪银纳米结构以增强二氧化碳还原：来自原位SERS和电化学研究的见解

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-12-10 DOI: 10.1016/j.apcata.2025.120743

E. Amaterz , O. Bajouk , B. Ravi , I. Rougeaux , R. Ramos , V. Faucheux , P. Chenevier

In this study, Ag structures with tunable morphologies were synthesized via different methods and evaluated for the electrochemical CO₂ reduction (CO₂RR) in both H-cell and zero-gap electrolyzer configurations. Scanning electron microscopy (SEM) confirmed that the Ag catalysts could be tuned to exhibit distinct morphologies, such as polygonal, flower-like, nanowires and rod-like structures. Among these, the rod-like Ag (Ag-Rod) catalyst exhibited the highest Faradaic efficiency for CO (>96 %), demonstrating excellent selectivity in both configurations. In-situ surface-enhanced Raman spectroscopy (SERS) was adopted to monitor the adsorption of reaction intermediates in real time, revealing dynamic changes in CO-related species and other adsorbates as a function of applied potential. The enhanced SERS response arising from the plasmonic properties of Ag enabled the direct observation of key reaction intermediates. The results show that the rod-like Ag structure exhibits superior CO selectivity, which is attributed to its morphology-dependent surface properties and favorable CO desorption dynamics. These findings highlight the critical role of structural tuning in governing CO₂RR pathways, providing mechanistic insight into how morphology and plasmonic effects can be leveraged to design efficient and selective Ag-based electrocatalysts for CO₂ conversion.

在本研究中，通过不同的方法合成了具有可调形貌的Ag结构，并对氢电池和零间隙电解槽配置下的电化学CO2还原（CO2RR）进行了评估。扫描电子显微镜（SEM）证实，Ag催化剂可以调整成不同的形态，如多边形、花状、纳米线和棒状结构。其中，棒状Ag （Ag- rod）催化剂对CO的法拉第效率最高（>96 %），在两种构型下均表现出优异的选择性。采用原位表面增强拉曼光谱（SERS）实时监测反应中间体的吸附情况，揭示co相关物质和其他吸附物随应用电位的动态变化。银的等离子体特性增强了SERS响应，从而可以直接观察关键的反应中间体。结果表明，棒状Ag结构表现出优异的CO选择性，这是由于其形貌依赖的表面性质和良好的CO脱附动力学。这些发现强调了结构调整在控制CO2RR途径中的关键作用，为如何利用形态和等离子体效应来设计高效和选择性的银基二氧化碳转化电催化剂提供了机制见解。

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引用次数: 0

Bimetallic ZnCo anchoring of Pt species in CTAB-modified silicalite-1 (S-1) zeolite for propane dehydrogenation ctab改性硅石-1 （S-1）分子筛中Pt的双金属锌钴锚定作用

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-12-10 DOI: 10.1016/j.apcata.2025.120720

Jie Zhou , Yuan Tao , Xiaohui He , Hongbing Ji

Constructing stable Pt-based catalysts for propane dehydrogenation (PDH) under harsh conditions remains a critical challenge due to the sintering and the migration of Pt species, and coke deposition, all of which contribute to the deactivation of catalysts. Herein, we report a novel catalyst with bimetallic ZnCo anchoring of Pt species encapsulated in CTAB-modified silicalite-1 (S-1) zeolite. This catalyst demonstrates exceptional PDH performance, maintaining a low deactivation rate constant of 0.0014 h⁻¹ after 115 h of operation at 550℃ under a pure propane stream. It achieves a stable propylene space-time yield (STY) of 35.6 mol

g_{Pt}^{- 1} h^{- 1}

, with a propane conversion of 25.6 % and a propene selectivity exceeding 98.0 %. The introduction of ZnCo bimetallic species promotes electron transfer, effectively inhibiting Pt sintering and regulating electronic structure of Pt species. Meanwhile, the incorporation of the soft template CTAB adjusts the structure of the channel of S-1 zeolite and contributes to the improvement of the catalyst durability. This synergistic design strategy offers a promising pathway for the development of robust and efficient PDH catalysts suited for industrial applications.

在恶劣条件下构建稳定的Pt基丙烷脱氢（PDH）催化剂仍然是一个关键的挑战，因为Pt的烧结和迁移以及焦炭的沉积都会导致催化剂失活。本文报道了一种新型催化剂，该催化剂将双金属zn - co锚定的Pt包裹在ctab修饰的硅-1 （S-1）沸石中。该催化剂表现出优异的PDH性能，在550℃纯丙烷流下运行115 h后，保持了0.0014 h−1的低失活速率常数。丙烯空时产率（STY）为35.6 mol gPt−1h−1，丙烯转化率为25.6%，丙烯选择性超过98.0%。ZnCo双金属组分的引入促进了电子转移，有效抑制了Pt烧结，调节了Pt组分的电子结构。同时，软模板CTAB的加入调整了S-1分子筛的通道结构，有助于提高催化剂的耐久性。这种协同设计策略为开发适合工业应用的稳健高效的PDH催化剂提供了一条有希望的途径。

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引用次数: 0

Effect of conductive polypyrrole on CuOx nanowire arrays for nitrate electroreduction to ammonia 导电聚吡咯对CuOx纳米线阵列硝酸电还原制氨的影响

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-12-04 DOI: 10.1016/j.apcata.2025.120742

Aijing Ma , Yuni Dewi Susanti , Xueqian Li , Dan Liu , Bhekie B. Mamba , Alex T. Kuvarega , Jianzhou Gui

Electrochemical nitrate reduction to ammonia (NRA) is recognized as a promising approach to address nitrate (NO₃^-) pollution while yielding high-value ammonia. However, the lack of efficient electrocatalysts has severely limited the development of this technology. In this study, conductive polypyrrole (PPy) modulated CuO_x nanowire arrays (CuO_x@PPy/CF) were elaborately designed, and the effect of PPy on NRA activity has been systematically investigated. The optimal CuO_x@PPy/CF-B2 electrocatalyst performed significantly better than the unmodified CuO_x/CF. It exhibited 96.52 % NO₃^- conversion, 99.76 % NH₄⁺ Faradaic efficiency, 93.28 % NH₄⁺ selectivity, and an NH₄⁺ yield of 0.249 mmol‧h⁻¹ ‧cm⁻². A series of characterizations confirmed that the porous PPy coating accelerated electron transfer and modulated the surface chemical microenvironment via promoting electrostatic adsorption of NO₃^- and accumulating hydrogenated species, thereby facilitating ammonia formation. Moreover, in situ ATR-FTIR spectroscopy identified reaction intermediates, enabling the proposal of a plausible reaction pathway. This work underscores the potential of conductive polymer-modified catalysts for advancing efficient nitrate electroreduction technology.

电化学硝酸还原制氨（NRA）被认为是解决硝态氮（NO3-）污染同时产生高价值氨的一种有前途的方法。然而，高效电催化剂的缺乏严重限制了该技术的发展。本研究精心设计了导电聚吡咯（PPy）调制的CuOx纳米线阵列（CuOx@PPy/CF），并系统研究了PPy对NRA活性的影响。优化后的CuOx@PPy/CF- b2电催化剂性能明显优于未改性的CuOx/CF。它的NO3-转化率为96.52 %，NH4+法拉第效率为99.76 %，NH4+选择性为93.28 %，NH4+产率为0.249 mmol·h⁻¹ ·cm−2。一系列表征证实了多孔PPy涂层通过促进NO3-的静电吸附和氢化物质的积累来加速电子转移和调节表面化学微环境，从而促进氨的形成。此外，原位ATR-FTIR光谱鉴定了反应中间体，从而提出了一个合理的反应途径。这项工作强调了导电聚合物改性催化剂在推进高效硝酸电还原技术方面的潜力。

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引用次数: 0

Photothermal catalytic reverse water-gas shift: Solar conversion mechanisms and catalyst design 光热催化反水气转换：太阳能转换机制和催化剂设计

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-12-03 DOI: 10.1016/j.apcata.2025.120741

Huijun Wang , Bin Cheng , Xi Chen , Xiaodong Ye , Jun Chen , Qun Chen , Junqing Ye

Carbon dioxide (CO₂), a prominent greenhouse gas, poses significant environmental challenges, including global warming and ecological disruption. The conversion of CO₂ into high-value-added products is imperative for achieving carbon peak and carbon neutrality goals. The reverse water-gas shift (RWGS) reaction, recognized as an efficient CO₂ conversion pathway, generates carbon monoxide (CO), which serves as a crucial feedstock for Fischer-Tropsch synthesis and as a versatile fuel. Recently, photothermal catalytic RWGS has emerged as a highly efficient alternative to conventional thermal catalysis and standalone photocatalysis, owing to its lower energy consumption and enhanced product selectivity. This review systematically examines recent advancements in photothermal catalytic RWGS, focusing on the classification of reaction mechanisms, including thermal-assisted photocatalysis (TAPC), photo-driven thermal catalysis (PDTC), and photo-thermal synergistic catalysis (PTSC). Additionally, it categorizes high-performance catalysts into three primary groups-noble and rare metal-based catalysts, non-noble metal-based catalysts, and metal-free catalysts. Representative examples are provided to illustrate the structure-activity relationships and catalytic performance. Ultimately, the review highlights the challenges and future directions in this field, aiming to deepen the mechanistic understanding and inspire the development of next-generation photothermal catalysts for sustainable CO₂ utilization.

二氧化碳（CO2）是一种重要的温室气体，对环境造成重大挑战，包括全球变暖和生态破坏。将二氧化碳转化为高附加值产品是实现碳峰值和碳中和目标的必要条件。逆向水气转换（RWGS）反应被认为是一种有效的二氧化碳转化途径，它产生一氧化碳（CO），一氧化碳是费托合成的重要原料，也是一种多功能燃料。近年来，光热催化RWGS因其较低的能耗和较高的产物选择性而成为传统热催化和独立光催化的高效替代品。本文系统地综述了光热催化RWGS的最新进展，重点介绍了反应机制的分类，包括热辅助光催化（TAPC）、光驱动热催化（PDTC）和光热协同催化（PTSC）。此外，它还将高性能催化剂分为三大类：贵金属和稀有金属基催化剂、非贵金属基催化剂和无金属催化剂。提供了代表性的例子来说明结构-活性关系和催化性能。最后，综述了该领域面临的挑战和未来的发展方向，旨在加深对机理的理解，促进下一代光热催化剂的开发，促进二氧化碳的可持续利用。

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引用次数: 0

NiMoO4 nanorods supported Ru clusters with improved catalytic activity for overall water splitting via enhanced metal support interaction NiMoO4纳米棒支持Ru团簇，通过增强金属支撑相互作用，提高了整体水分解的催化活性

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-12-02 DOI: 10.1016/j.apcata.2025.120733

Junfei Zhao, Siru Chen, Zhuohan Zhang, Xiaoyu Song, Yanjie Wang, Jiabin Xiong, Yaomin Zhao

The development of efficient and durable bifunctional electrocatalysts is crucial for sustainable hydrogen production via electrochemical water splitting. This work presents the rational design and synthesis of Ru nanoclusters anchored on NiMoO₄ nanorods (Ru- NiMoO₄) as a high-performance catalyst for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). The composite leverages the inherent OER activity of the NiMoO₄ support, the high intrinsic HER activity of Ru nanoclusters, and critically, enhanced electronic metal-support interaction (EMSI). Detailed characterization confirms the successful formation of highly dispersed Ru nanoclusters on the NiMoO₄ nanorods and reveals electronic structure modulation. The optimized catalyst Ru-NiMoO₄-2 requires remarkably low overpotentials of only 56 mV for HER and 318 mV for OER to achieve 10 mA cm⁻² in 1.0 M KOH, with good stability. When employed as both anode and cathode in a two-electrode electrolyzer, it delivers a current density of 10 mA cm⁻² at a low cell voltage of 1.638 V with near-unity Faradaic efficiency. This work highlights the efficacy of strategic support selection and harnessing EMSI for designing advanced bifunctional electrocatalysts for efficient overall water splitting.

开发高效、耐用的双功能电催化剂是实现电化学水分解制氢的关键。本文介绍了基于NiMoO4纳米棒的Ru纳米团簇（Ru- NiMoO4）作为析氢反应（HER）和析氧反应（OER）的高性能催化剂的合理设计和合成。该复合材料利用了NiMoO4载体固有的OER活性，Ru纳米团簇的高固有HER活性，以及增强的电子金属-载体相互作用（EMSI）。详细的表征证实了在NiMoO4纳米棒上成功形成了高度分散的Ru纳米团簇，并揭示了电子结构的调制。优化后的Ru-NiMoO4-2催化剂在1.0 M KOH条件下，HER过电位仅为56 mV， OER过电位仅为318 mV，达到10 mA cm−2，稳定性良好。当在双电极电解槽中作为阳极和阴极时，它在1.638 V的低电池电压下提供10 mA cm−2的电流密度，具有接近单位的法拉第效率。这项工作强调了战略支持选择的有效性，并利用EMSI来设计先进的双功能电催化剂，以实现高效的整体水分解。

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引用次数: 0

Polyaniline-derived B/N-doped carbon supporting isolated Pd and Au nanoparticles as a bimetal catalyst for high-performance 4-chloronitrobenzene hydrogenation 聚苯胺衍生的B/ n掺杂碳负载分离Pd和Au纳米颗粒作为高性能4-氯硝基苯加氢的双金属催化剂

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-12-02 DOI: 10.1016/j.apcata.2025.120740

Qingtai Xie , Libo Sun , Zhiyuan Xu, Heshun Jing, Caixia Qi, Baorong Duan, Xun Sun, Lijun Zhao, Miao Zhang, Xiaolong Zhang

The study describes the fabrication of a 0.05 %Pd-0.5 %Au bimetallic nanocatalyst supported on B/N-doped carbon (BNC) for chemoselective reduction of 4-chloronitrobenzene (p-CNB) yielding 4-chloroaniline (p-CAN) as the major product. The BNC support was synthesized via pyrolysis of boric acid-doped polyaniline, followed by the loading of isolated Pd and Au nanoparticles as a bimetal catalyst through sol-immobilization. Characterization revealed that B doping induced electron deficiency in Au and Pd nanoparticles, enhancing p-CNB adsorption. The catalyst exhibited exceptional low-temperature activity (100 % conversion, 90 % selectivity at 60 °C) and stability (only a 16 % decrease in conversion after 5 cycles). Temperature-programmed desorption (TPD) confirmed synergistic Lewis acid-base sites on BNC, enabling efficient H₂ activation. With an apparent activation energy (E_a) of 16.9 kJ/mol and turnover frequency (TOF) of 5176 h⁻¹, 0.05 %Pd-0.5 %Au/BNC demonstrated superior performance under milder conditions compared with reported systems. The findings highlighted the critical role of heteroatom-induced electronic modulation in optimizing catalytic efficiency for industrial hydrogenation processes.

研究制备了一种以掺杂B/ n碳（BNC）为载体的0.05 %Pd-0.5 %Au双金属纳米催化剂，用于化学选择性还原4-氯硝基苯（p-CNB），主要产物为4-氯苯胺（p-CAN）。通过热解硼酸掺杂聚苯胺合成BNC载体，然后通过溶胶固定化负载分离的钯和金纳米颗粒作为双金属催化剂。表征表明，B掺杂导致Au和Pd纳米粒子的电子缺乏，增强了对p-CNB的吸附。该催化剂表现出优异的低温活性（转化率为100% %，60°C时选择性为90% %）和稳定性（循环5次后转化率仅下降16% %）。程序升温解吸（TPD）证实了BNC上Lewis酸碱位点的协同作用，实现了高效的H2活化。表观活化能（Ea）为16.9 kJ/mol，周转率（TOF）为5176 h−1,0.05 %Pd-0.5 %Au/BNC在较温和的条件下表现出较好的性能。这些发现突出了杂原子诱导的电子调制在优化工业加氢过程的催化效率方面的关键作用。

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