Catalysis Science & Technology最新文献_第2页

Adsorption or photocatalysis? Engineering BiOI with metalorganic framework CAU-17 and microporous organic polymer MOP-CH2EDA to enhance ciprofloxacin removal from water 吸附还是光催化？利用金属有机骨架cac -17和微孔有机聚合物mopp - ch2eda来提高水中环丙沙星的去除效果

IF 4 3区化学 Q2 CHEMISTRY, PHYSICAL

Catalysis Science & Technology

Pub Date : 2026-06-22 Epub Date: 2026-05-14 DOI: 10.1039/d6cy00135a

Sepideh G. Khasevani, Saulius Kaciulis, Alessio Mezzi, Shokat Sarmad, Jyri-Pekka Mikkola, Dariush Nikjoo, Isabella Concina

This work reports the design of binary and ternary BiOI-based composites incorporating the metal–organic framework CAU-17 and the amine-functionalized microporous organic polymer MOP-CH₂EDA for the removal of ciprofloxacin (CIP) from water. The materials were synthesized via an in situ solvothermal approach and systematically characterized to establish structure–property relationships. The results reveal that adsorption and photocatalysis act as coupled and sequential processes, rather than independent pathways, with the polymer component enhancing CIP pre-concentration and the BiOI/MOF interface governing photodegradation. The ternary composite BCM-10% exhibited the best performance, achieving up to 80% CIP removal under simulated solar irradiation. Scavenger experiments indicate that ·O₂⁻ is the dominant reactive species, while photogenerated holes also contribute significantly. The degradation process is strongly influenced by pH, reflecting the interplay between catalyst surface properties, reactive oxygen species generation, and CIP speciation. HPLC-MS analysis confirms the formation of multiple intermediates and highlights the complexity of the degradation pathways. Despite the improved performance of the ternary composites, the overall activity remains moderate compared to state-of-the-art photocatalysts, underscoring the limitations of current BiOI-based systems. The results emphasize that apparent kinetic behavior is strongly affected by adsorption contributions, complicating direct comparison with literature data. This study provides new insight into the design of multifunctional materials for water treatment, highlighting the importance of adsorption–photocatalysis synergy and the need for more rigorous and standardized evaluation of photocatalytic systems.

本文报道了一种基于金属有机骨架cac -17和胺功能化微孔有机聚合物mopp - ch2eda的二元和三元生物基复合材料的设计，用于去除水中的环丙沙星（CIP）。采用原位溶剂热法合成了该材料，并对其进行了系统表征，建立了结构-性能关系。结果表明，吸附和光催化是一个耦合的、连续的过程，而不是独立的过程，聚合物组分增强了CIP预富集，而BiOI/MOF界面控制了光降解。在模拟太阳辐照下，三元复合材料BCM-10%的CIP去除率最高可达80%。清道夫实验表明，·O2−是主要的反应物质，光生空穴也起着重要作用。降解过程受pH的强烈影响，反映了催化剂表面性质、活性氧生成和CIP形态之间的相互作用。HPLC-MS分析证实了多种中间体的形成，并强调了降解途径的复杂性。尽管三元复合材料的性能有所提高，但与最先进的光催化剂相比，其总体活性仍然适中，这突出了当前基于bioi的系统的局限性。结果强调表观动力学行为受到吸附贡献的强烈影响，使与文献数据的直接比较复杂化。该研究为水处理多功能材料的设计提供了新的见解，突出了吸附-光催化协同作用的重要性，以及对光催化系统进行更严格和标准化评估的必要性。

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引用次数: 0

Ru/CeO2 catalysts for supercritical water gasification of glycerol: stability, activity, and coke hydrothermal oxidation Ru/CeO2超临界水气化甘油催化剂：稳定性、活性及焦炭水热氧化

IF 4 3区化学 Q2 CHEMISTRY, PHYSICAL

Catalysis Science & Technology

Pub Date : 2026-06-22 Epub Date: 2026-05-29 DOI: 10.1039/d5cy01486g

Tomasz Kondratowicz, Aurélien Quenet, Xujun Li, Andrea Testino, Oliver Kröcher, Frédéric Vogel, David Baudouin

Cerium oxide (CeO₂) was investigated as a support for Ru nanoparticles in the continuous supercritical water gasification (SCWG) of glycerol as a model biomass compound. The stability of pure CeO₂ under reductive SCW conditions was first assessed in both batch and continuous modes. In batch, CeO₂ readily underwent phase transformation to CeCO₃OH, implying reduction of Ce⁴⁺ to Ce³⁺, leading to severe loss of surface area. The formation of CeCO₃OH was completely prevented in continuous flow due to the flushing of CO₂ and reductive compounds before cooling down to a temperature thermodynamically favouring CeCO₃OH. Although pristine CeO₂ showed low activity in SCWG, thermal treatment strongly influenced product distribution, with CO disappearing in favour of C₃H₈ after a reductive pretreatment. When Ru nanoparticles were supported on thermally stabilized CeO₂ (calcined at 700–900 °C, 0.11–1.00 wt% Ru), the catalysts displayed high efficiency in SCWG of glycerol, yielding CO₂, CH₄, and H₂ as the main products. These Ru/CeO₂ catalysts achieved apparent conversion rates up to three times higher than a commercial 5 wt% Ru/AC benchmark, while maintaining similar selectivity trends. Both Ru/CeO₂ and carbon-based catalysts exhibited similar decreasing activity trends under operation. Post-reaction analysis revealed some carbon deposition on Ru/CeO₂, likely the main cause of the observed loss of activity, which could be effectively removed either by thermal oxidation in air at 300 °C or by in situ hydrothermal oxidation with H₂O₂ at 110 °C. Overall, Ru/CeO₂ emerges as a durable and regenerable alternative to Ru/carbon for SCWG applications.

研究了氧化铈（CeO2）作为Ru纳米颗粒在甘油连续超临界水气化（SCWG）中的载体。首先在间歇和连续两种模式下评估了纯CeO2在还原性SCW条件下的稳定性。在批处理过程中，CeO2很容易相变为CeCO3OH，这意味着Ce4+被还原为Ce3+，导致了严重的表面积损失。在冷却到热力学上有利于CeCO3OH的温度之前，由于CO2和还原性化合物的冲洗，在连续流动中完全阻止了CeCO3OH的形成。虽然原始的CeO2在SCWG中表现出较低的活性，但热处理对产物分布有很大的影响，在还原预处理后，CO消失，取而代之的是C3H8。当Ru纳米颗粒负载在热稳定的CeO2（700 ~ 900℃，0.11 ~ 1.00 wt% Ru）上时，催化剂在甘油的SCWG中表现出较高的效率，主要产物为CO2、CH4和H2。这些Ru/CeO2催化剂的表观转化率比商用5 wt% Ru/AC基准高出3倍，同时保持了相似的选择性趋势。Ru/CeO2和碳基催化剂在运行过程中表现出相似的活性下降趋势。反应后分析表明，Ru/CeO2表面有碳沉积，这可能是导致活性损失的主要原因，可以通过300℃的空气热氧化或110℃的H2O2原位水热氧化来有效去除。总的来说，Ru/CeO2是一种耐用且可再生的SCWG应用中Ru/碳的替代品。

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引用次数: 0

Tailored synthesis of hollow tubular In2O3/In2S3 Z-scheme heterojunctions for highly selective CO production in CO2 hydrogenation 在CO2加氢过程中高选择性产CO的中空管状In2O3/In2S3 z -方案异质结的定制合成

IF 4 3区化学 Q2 CHEMISTRY, PHYSICAL

Catalysis Science & Technology

Pub Date : 2026-06-22 Epub Date: 2026-05-19 DOI: 10.1039/d6cy00306k

Fenghao Xing, Qiutong Han, Lei Wang, Buyun Shi, Chuqiu Wang, Yichang Pan

Efficient CO₂ hydrogenation to value-added CO under mild conditions is critical for carbon neutrality. Herein, we report a hollow tubular In₂O₃/In₂S₃ Z-scheme heterojunction catalyst, synthesized via sulfidation of a MOF-derived In₂O₃ nanotube precursor. Under atmospheric pressure and low temperature (180 °C), the catalyst achieves highly selective CO production (96.35% selectivity) with a CO production rate of 122.80 μmol g⁻¹ h⁻¹ in photothermal catalytic CO₂ reduction-exceeding those of pure In₂O₃ and bulk In₂O₃ by 5.85- and 27.91-fold, respectively. The hollow tubular architecture enhances mass transfer and exposes abundant active sites, while the In₂O₃/In₂S₃ interface enables efficient charge separation via a Z-scheme mechanism. The photothermal synergistic effect further accelerates reaction kinetics and lowers the reaction energy barrier, collectively improving both the yield and selectivity of the products.

在温和的条件下，有效的二氧化碳加氢为增值CO是碳中和的关键。在此，我们报道了一种空心管In2O3/In2S3 Z-scheme异质结催化剂，通过mof衍生的In2O3纳米管前驱体的硫化合成。在常压和低温（180℃）条件下，该催化剂在光热催化CO2还原过程中，CO产率为122.80 μmol g−1 h−1，达到了高选择性CO产率（96.35%），分别是纯In2O3和本体In2O3的5.85倍和27.91倍。空心管结构增强了传质，暴露了丰富的活性位点，而In2O3/In2S3界面通过Z-scheme机制实现了有效的电荷分离。光热协同效应进一步加速了反应动力学，降低了反应能垒，共同提高了产物的收率和选择性。

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引用次数: 0

Engineering and optimising barium cerate-supported cobalt catalyst for ammonia synthesis 工程和优化铈酸钡负载的合成氨钴催化剂

IF 4 3区化学 Q2 CHEMISTRY, PHYSICAL

Catalysis Science & Technology

Pub Date : 2026-06-22 Epub Date: 2026-05-26 DOI: 10.1039/d5cy01610j

Hubert Ronduda, Małgorzata Lemańska, Urszula Ulkowska, Wojciech Patkowski, Weronika Bulejak, Andrzej Ostrowski, Jacek Sikorski, Kamil Sobczak, Milena Ojrzyńska, Dariusz Moszyński, Wioletta Raróg-Pilecka

Ammonia synthesis under mild reaction conditions remains a key challenge to realising a carbon-free society. The development of efficient catalysts for ammonia synthesis is therefore of great interest nowadays. Here, the effects of the cobalt deposition method and loading on the physicochemical properties and catalytic performance of Sm-doped BaCeO₃-supported Co catalysts were systematically investigated. Catalysts were prepared by deposition–precipitation, wet impregnation, and physical mixing methods. Depending on the method used, the catalyst properties varied in terms of chemisorptive properties and catalytic activity. The favourable activity observed for catalysts prepared by deposition–precipitation and wet impregnation methods was attributed to a more diverse surface landscape that facilitates hydrogen and nitrogen adsorption and activation. Then, by using the deposition–precipitation method, a series of catalysts with Co loadings from 10 to 50 wt% was synthesised. Catalytic testing revealed a clear dependence of activity on Co loading, with the highest reaction rate and intrinsic turnover frequency observed for the catalyst loaded with 40 wt% Co. This behaviour was explained not only by the greater number of adsorption sites but also by the structural sensitivity of cobalt in ammonia synthesis, where a diverse surface landscape with various adsorption sites improved the catalytic performance.

温和反应条件下的氨合成仍然是实现无碳社会的关键挑战。因此，开发高效的氨合成催化剂是目前人们非常关心的问题。本文系统研究了钴沉积方式和负载对sm掺杂baceo3负载Co催化剂的理化性质和催化性能的影响。采用沉积沉淀法、湿浸渍法和物理混合法制备了催化剂。根据使用的方法，催化剂的性质在化学吸附性质和催化活性方面有所不同。沉积沉淀法和湿浸渍法制备的催化剂具有良好的活性，这是因为其表面景观更多样化，有利于氢和氮的吸附和活化。然后，采用沉积-沉淀法，合成了一系列Co载重在10% ~ 50%之间的催化剂。催化测试表明，活性明显依赖于Co负载，当Co负载为40 wt%时，反应速率和固有循环频率最高。这种行为不仅可以解释为更多的吸附位点，还可以解释为氨合成中钴的结构敏感性，其中不同的表面景观和不同的吸附位点提高了催化性能。

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引用次数: 0

Trace palladium and copper as hidden catalysts in cross-coupling reactions: roles and analytical detection 痕量钯和铜作为交叉偶联反应的隐藏催化剂：作用和分析检测

IF 4 3区化学 Q2 CHEMISTRY, PHYSICAL

Catalysis Science & Technology

Pub Date : 2026-06-22 Epub Date: 2026-05-13 DOI: 10.1039/d6cy00003g

Papita Behera, Santosh Kumar Sahu, Pradyota Kumar Behera, Laxmidhar Rout, Debendra Kumar Mohapatra

Palladium- and copper-catalyzed reactions are among the most widely employed methodologies in cross-coupling chemistry for the formation of key C–X (X = C, N, O, S) bonds, underpinning the synthesis of pharmaceuticals, agrochemicals, and complex natural products. Considerable efforts have been directed toward developing alternative catalytic systems based on inexpensive metals or organocatalysis; however, many such systems, including those reported as metal-free, are often not truly devoid of ultra-trace amounts of palladium and copper at ppm, ppb, or even ppt levels. This Review highlights systematic approaches for the detection and removal of hidden Pd/Cu impurities that can lead to misinterpretation of metal-free reactivity. It further examines how ultra-low loadings of these metals can still deliver high turnover numbers (TON), thereby influencing mechanistic understanding. This review article also provides a comprehensive framework for identifying trace Pd/Cu metal impurities and elucidating their unnoticed roles in cross-coupling chemistry.

钯和铜催化反应是交叉偶联化学中最广泛使用的方法之一，用于形成关键的C - X （X = C， N， O， S）键，支持药物，农用化学品和复杂天然产物的合成。在开发基于廉价金属或有机催化的替代催化系统方面已经做出了相当大的努力；然而，许多这样的系统，包括那些被报道为无金属的系统，通常并不是真正不含ppm、ppb甚至PPT水平的超痕量钯和铜。这篇综述强调了检测和去除隐藏的Pd/Cu杂质的系统方法，这些杂质可能导致对无金属反应性的误解。它进一步研究了这些金属的超低负荷如何仍然可以提供高周转率（TON），从而影响机理理解。本文还提供了鉴定痕量Pd/Cu金属杂质和阐明其在交叉偶联化学中未被注意的作用的综合框架。

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引用次数: 0

Synthesis of ethanol via methanol homologation with CO2 and H2 using an industrially relevant Ru–Co catalyst 使用工业上相关的Ru-Co催化剂，通过甲醇与CO2和H2的同源性合成乙醇

IF 4 3区化学 Q2 CHEMISTRY, PHYSICAL

Catalysis Science & Technology

Pub Date : 2026-06-22 Epub Date: 2026-05-18 DOI: 10.1039/d6cy00285d

Longbo Zhang, Jia Guo, Yanyan Wang, Ying Wang, Jie Li, Hongxing Wang, Chenglong Yu, Yanru Zhang, Jun He, Xianyu Meng, Zhuo Zhang, Tianbin Wu, Qingli Qian, Li Tan, Buxing Han

Homogeneously catalyzed ethanol synthesis from CO₂ and H₂ usually uses expensive, unstable and complex catalyst precursors, hindering their industrial viability. In this work, a homogeneous catalytic system consisting of economic and stable catalyst precursors (RuCl₃·3H₂O and CoCl₂·6H₂O), cocatalyst (LiI) and N-ethyl-2-pyrrolidone (NEP) solvent was designed to accelerate ethanol production via methanol homologation with CO₂ and H₂. After activation of the catalyst precursors at 200 °C with CO, the target reaction could proceed efficiently under mild conditions (170 °C), with top level reaction selectivity (64.9%) and much higher space time yield (STY) of ethanol (3.9 g L⁻¹ h⁻¹) compared to previous reports with Ru/Co catalysts. The impact of activation conditions, reaction conditions, and the catalytic mechanism of the reaction were studied by a series of control experiments. This method of ethanol production has the advantages of a stable and easily available catalyst, excellent performance, and easy separation and recycling of the catalyst, showing great potential for industrialization.

均相催化CO2和H2合成乙醇通常使用昂贵、不稳定和复杂的催化剂前体，阻碍了其工业可行性。本研究设计了一个由经济稳定的催化剂前驱体（RuCl3·3H2O和CoCl2·6H2O）、助催化剂（LiI）和n -乙基-2-吡咯烷酮（NEP）溶剂组成的均相催化体系，通过甲醇与CO2和H2的同质化来加速乙醇的生产。催化剂前驱体在200℃用CO活化后，目标反应可以在温和条件下（170℃）高效进行，反应选择性达到最高水平（64.9%），乙醇的时空产率（STY）（3.9 g L−1 h−1）比之前报道的Ru/ CO催化剂高得多。通过一系列的对照实验，研究了活化条件、反应条件和催化机理对反应的影响。该方法生产乙醇具有催化剂稳定易得、性能优异、催化剂易于分离和回收等优点，具有很大的工业化潜力。

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引用次数: 0

Dual Pd2+ and Pd0 sites on CeO2 for selective oxidative cleavage of C–C bonds in lignin β-O-4 ketones 木质素β-O-4酮的C-C键选择性氧化裂解在CeO2上的双Pd2+和Pd0位点

IF 4 3区化学 Q2 CHEMISTRY, PHYSICAL

Catalysis Science & Technology

Pub Date : 2026-06-22 Epub Date: 2026-05-12 DOI: 10.1039/d6cy00428h

Yuzhen Hu, Ruiying Xiong, Xin Qu, Taras Nagornyy, Zhenlong Song, Xingye Zeng, Ning Li, Qi Zhang, Longlong Ma

Selective C–C bond cleavage in lignin is a pivotal step toward its efficient utilization, enabling the production of diverse and valuable chemicals from this abundant and renewable resource. Among the catalysts reported for the oxidative cleavage of C–C bonds in lignin β-O-4 ketones, CeO₂-supported Pd catalysts have demonstrated outstanding activity. However, the exact nature of the active Pd sites responsible for the C–C bond cleavage remains poorly understood, limiting mechanistic insights into this transformation. In this study, CeO₂ supports with four distinct morphologies including rods (R), spheres (S), cubes (C), and polyhedrons (P) were synthesized to investigate their influence on the catalytic activity of Pd/CeO₂ catalysts in the oxidative cleavage of β-O-4 ketones. The catalytic performance was found to depend strongly on the morphology of CeO₂, with Pd/CeO₂-P exhibiting the highest activity for the C–C bond cleavage. This catalyst possessed the lowest Pd⁴⁺ content and the highest Pd⁰/Pd²⁺ ratio among the series. By systematically tuning this ratio, a volcano-type relationship between the Pd⁰/Pd²⁺ ratio and catalytic activity was established, indicating a dual-site mechanism in which Pd⁰ facilitates the formation of reactive oxygen species, while Pd²⁺ serves as the active center for the C–C bond cleavage.

木质素中C-C键的选择性裂解是实现其高效利用的关键一步，使这种丰富的可再生资源能够生产出多种有价值的化学品。在已报道的木质素β-O-4酮C-C键氧化裂解催化剂中，ceo2负载的Pd催化剂表现出优异的活性。然而，负责C-C键裂解的活性Pd位点的确切性质仍然知之甚少，限制了对这种转化的机制见解。本研究合成了棒状(R)、球状(S)、立方体(C)和多面体(P)四种不同形态的CeO2载体，研究了它们对Pd/CeO2催化剂氧化裂解β-O-4酮催化活性的影响。催化性能与CeO2的形态密切相关，其中Pd/CeO2- p对C-C键的裂解活性最高。该催化剂具有最低的Pd4+含量和最高的Pd0/Pd2+比。通过系统调整该比值，建立了Pd0/Pd2+比值与催化活性之间的火山型关系，表明Pd0促进活性氧的形成，而Pd2+则是C-C键裂解的活性中心。

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引用次数: 0

Ambient pressure ammonia decomposition using Ga–Co supported catalytically active liquid metal solutions 使用Ga-Co负载的催化活性液态金属溶液进行常压氨分解。

IF 4 3区化学 Q2 CHEMISTRY, PHYSICAL

Catalysis Science & Technology

Pub Date : 2026-06-22 Epub Date: 2026-06-06 DOI: 10.1039/d6cy00362a

Philipp Rothgängel, Nicola Taccardi, Aaron Luke Folkard, Jakob Söllner, Alexander Søgaard, Andreas Körner, Andreas Hutzler, Matthias Thommes, Marco Haumann, Peter Wasserscheid

Ga–Co supported catalytically active metal solutions (SCALMS) on silicon carbide (SiC) were successfully tested for ambient pressure ammonia decomposition in the temperature range between 480 and 580 °C. Comparison studies of a Ga₅₉Co SCALMS system with their monometallic equivalents Co/SiC and Ga/SiC revealed a massively enhanced ammonia decomposition activity of the supported alloy catalyst. The Ga₅₉Co/SiC outperformed a monometallic benchmark Co/SiC catalyst in terms of the Co specific H₂ productivity by up to one order of magnitude. Monometallic Ga/SiC, in contrast, showed no activity for ammonia decomposition up to 580 °C. We report productivities of 487 g_H₂ g_Co⁻¹ h⁻¹ at 5% conversion and 550 °C at a weight hourly space velocity (WHSV) of 29 000 mL_N g_cat⁻¹ h⁻¹ for our SCALMS system. Apparent activation energies (E_A,app) determined from temperature variation experiments give no indication for diffusion limitations under the applied reaction conditions. Therefore, we present a new catalyst material concept for ammonia decomposition with high potential for practical and technical application.

在碳化硅（SiC）上成功测试了Ga-Co负载的催化活性金属溶液（SCALMS）在480 - 580°C的环境压力下的氨分解。对Ga59Co SCALMS体系与Co/SiC和Ga/SiC的单金属当量进行了对比研究，发现负载合金催化剂的氨分解活性大大增强。在Co比H2产率方面，Ga59Co/SiC优于单金属基准Co/SiC催化剂，最高可达一个数量级。相比之下，单金属的Ga/SiC在580℃以上没有氨分解活性。我们报告了我们的SCALMS系统在5%转化率和550°C下的产量为487 gH2 gCo -1 h-1，重量小时空速（WHSV）为29 000 mLN gcat -1 h-1。由温度变化实验确定的表观活化能（ea,app）并没有表明在应用反应条件下的扩散限制。因此，我们提出了一种具有实际和技术应用潜力的氨分解催化剂材料新概念。

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引用次数: 0

On the reactions of (hetero)aryl and vinyl triflates with [Ni(COD)(dppf)] （杂）芳基和三氟乙烯酯与[Ni(COD)(dppf)]的反应

IF 4 3区化学 Q2 CHEMISTRY, PHYSICAL

Catalysis Science & Technology

Pub Date : 2026-06-22 Epub Date: 2026-05-19 DOI: 10.1039/d6cy00261g

Nicholas C. C. McVeigh, Megan E. Greaves, Rachel H. Munday, Thomas O. Ronson, Scott Rice, Stephen Sproules, David J. Nelson

We report the experimental and computational investigations of the reactions of aryl, heteroaryl, and vinyl triflates with a model nickel(0) complex. While the reactions of most (hetero)aryl and vinyl triflates behave straightforwardly, the reactions of 2-pyridinyl triflates are rather different; under reaction conditions where the organotriflates are used in vast excess there is not a simple pseudo-first order behaviour. These reactions are further explored using DFT calculations, which show that both three- and five-centred oxidative addition transition states are viable, but that the experimentally-observed order of reactivity is not readily reproduced by considering a simple oxidative addition pathway.

我们报道了芳基、杂芳基和三氟乙烯酯与模型镍(0)配合物反应的实验和计算研究。大多数（杂）芳基和乙烯基三氟酸酯的反应是直接的，而2-吡啶基三氟酸酯的反应则是相当不同的；在大量过量使用有机三酸酯的反应条件下，不存在简单的伪一阶行为。使用DFT计算进一步探索了这些反应，结果表明三中心和五中心的氧化加成过渡态都是可行的，但通过考虑简单的氧化加成途径，实验观察到的反应性顺序不易再现。

引用次数: 0

Steering C–C bond cleavage and hydrogenation in polystyrene hydrocracking through external Brønsted acid sites over Ni/zeolites 在Ni/沸石上通过外部Brønsted酸位控制聚苯乙烯加氢裂化过程中C-C键的解理和加氢

IF 4 3区化学 Q2 CHEMISTRY, PHYSICAL

Catalysis Science & Technology

Pub Date : 2026-06-22 Epub Date: 2026-04-13 DOI: 10.1039/d6cy00204h

Jonghyun Park, Taeeun Kwon, Ki Hyuk Kang, Wangyun Won, Insoo Ro

Unlike polyolefin hydrocracking, aromatic substituents in polystyrene (PS) stabilize benzylic species and redirect degradation pathways, making selective catalytic upcycling more difficult. Consistent with this challenge, recycling rates for polyolefins reach only 5.3–10.3%, whereas PS remains below 1%. Here, PS hydrocracking over bifunctional Ni/zeolite catalysts was examined to determine how hydrogen utilization and C–C bond cleavage depend on Brønsted acid sites (BASs) and the accessibility of active sites to polymer-derived intermediates. Non-acidic Ni catalysts mainly consumed hydrogen via aromatic-ring hydrogenation with minimal PS conversion, whereas incorporating BASs enabled depolymerization under mild conditions (300 °C). Across HY zeolites and additional frameworks with similar SiO₂/Al₂O₃ ratios, conversion exhibited non-monotonic behavior: excessive acidity and/or restricted polymer accessibility reduced activity, yielding volcano-like trends and framework-dependent deviations. Poisoning tests indicated that external BASs are required to initiate backbone cleavage. Product distributions further reflected the interplay between acid-site accessibility and hydrogenation capacity, and hydrogen consumption correlated linearly with PS conversion within the Ni/zeolite series. Overall, these results highlight externally accessible Brønsted acidity as a practical handle for tuning Ni/zeolite catalysts toward LOHC-relevant products.

与聚烯烃加氢裂化不同，聚苯乙烯（PS）中的芳香族取代基稳定了苯类物质并改变了降解途径，使得选择性催化升级回收变得更加困难。与这一挑战相一致的是，聚烯烃的回收率仅为5.3-10.3%，而PS的回收率仍低于1%。本文研究了双功能Ni/沸石催化剂上的PS加氢裂化，以确定氢利用和C-C键裂解如何依赖于Brønsted酸位点（BASs）和活性位点对聚合物衍生中间体的可及性。非酸性Ni催化剂主要通过芳香环加氢消耗氢，PS转化率极低，而加入BASs则能在温和条件下（300°C）解聚。在SiO2/Al2O3比例相似的HY沸石和其他框架中，转化表现出非单调行为：酸度过高和/或聚合物可及性受限，活性降低，产生类似火山的趋势和框架依赖的偏差。中毒试验表明，需要外部BASs来启动骨干劈裂。产物分布进一步反映了酸位可及性与加氢能力之间的相互作用，氢消耗与Ni/沸石系列中PS转化率呈线性相关。总的来说，这些结果强调了外部可访问的Brønsted酸度是将Ni/沸石催化剂调整为lohc相关产品的实用手柄。

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引用次数: 0