Applied Catalysis A: General最新文献_第2页

Pd-loaded two-dimensional NiO nanosheet zeolite catalyst for selective hydrogenolysis of sorbitol to produce 1,2-propanediol and ethylene glycol 负载pd的二维NiO纳米片分子筛催化剂用于山梨醇选择性氢解制备1,2-丙二醇和乙二醇

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-01-21 DOI: 10.1016/j.apcata.2026.120797

Haodong Huang , Bo Chen , Zhiwei Zheng , Changyi Chen , Ruifeng Luo , Haijun Guo , Zhili Li , Xinde Chen

1,2-propanediol (1,2-PDO) and ethylene glycol (EG), as key precursors for high-value fine chemicals, represent one of the core challenges in green chemical engineering through the development of biomass-directed conversion systems. This study constructed a bifunctional x%NiO@Hβ-1 %Pd hierarchical porous catalyst through an interfacial engineering strategy: utilizing the confinement effect of two-dimensional mesoporous nickel silicate nanosheets to load Ni onto Hβ zeolite, and anchored highly dispersed Pd nanoparticles on the NiO@Hβ surface through NaBH₄-induced in situ reduction, systematically investigated the structure-activity relationship of this catalyst for sorbitol hydrogenolysis in Ca(OH)₂ alkaline aqueous systems. Combined NH₃-TPD and N₂ adsorption-desorption characterization revealed that, the introduction of Hβ zeolite significantly modulated the catalyst acidity and pore structure—the total acid amount of 25 %NiO@Hβ-1 %Pd reached 4.13 mmol/g (representing a 104 % enhancement compared to the support-free system), the desorption peak at 550°C corresponds to strong Lewis acid sites formed by Ni-O-Si bonds, the pore system with 69 % mesopore content (BET specific surface area of 541.6 m²/g) provides efficient transport pathways for reactant diffusion. Mechanistic studies revealed that, the Brønsted acid sites of Hβ selectively adsorb sorbitol C-O bonds through hydrogen bonding interactions, while spillover hydrogen species at the Pd-Ni interface synergistically induce selective C-C bond cleavage in cooperation with strong Lewis acid sites, ultimately achieved a total diol carbon yield of 80.3 C% for 1,2-PDO/EG under conditions of 220°C and 3 MPa H₂. This work provides new insights into the “acid-metal-mass transfer” ternary synergistic mechanism for precise hydrogenolysis of biomass polyols.

1,2-丙二醇（1,2- pdo）和乙二醇（EG）作为高价值精细化学品的关键前体，是发展生物质定向转化系统的绿色化学工程的核心挑战之一。本研究通过界面工程策略构建了双功能x%NiO@Hβ-1 %Pd分层多孔催化剂：利用二维介孔硅酸镍纳米片的约束效应将Ni负载到Hβ分子筛上，并通过nabh4诱导的原位还原将高度分散的Pd纳米颗粒锚定在NiO@Hβ表面，系统地研究了该催化剂在Ca(OH)2碱性水体系中山梨糖醇氢解的结构-活性关系。结合NH3-TPD和N2吸附-解吸表征表明，Hβ分子筛的引入显著调节了催化剂的酸性和孔结构，总酸量为25 %NiO@Hβ-1 %Pd达到4.13 mmol/g（比无载体体系提高了104 %），550℃时的解吸峰对应于Ni-O-Si键形成的强Lewis酸位点；介孔含量为69 % （BET比表面积为541.6 m2/g）的孔隙体系为反应物扩散提供了有效的传输途径。机理研究表明，Hβ的br约nsted酸位点通过氢键相互作用选择性吸附山梨醇C- o键，而Pd-Ni界面的溢出氢与强Lewis酸位点协同诱导选择性C-C键裂解，最终在220℃和3 MPa H2条件下，1,2- pdo /EG的总二醇碳收率为80.3 C%。这项工作为生物质多元醇精确氢解的“酸-金属-传质”三元协同机制提供了新的见解。

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引用次数: 0

Dehydrofluorination of 1,1,1,2-tetrafluoroethane to 1,1,2-trifluoroethylene by Ce-F-Al active center over NiAl spinel 在NiAl尖晶石上用Ce-F-Al活性中心将1,1,1,2-四氟乙烷脱氢氟化为1,1,2-三氟乙烯

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-01-20 DOI: 10.1016/j.apcata.2026.120796

Sihui Wu , Bing Liu , Fangcao Liu , Hong Yang , Zhanwang Li , Yuncong Xu , Mingyue Wang , Wenfeng Han

Conversion of potent greenhouse gases, hydrofluorocarbons (HFCs), to value-added hydrofluoroolefins (HFOs) is of great importance. To address the issue of carbon deposition associated with strong Lewis acid sites during the conversion process, this study introduces a Ce source to modify the surface acid structure of NiAl spinel. A series of Ce loading NiAl oxide catalysts were synthesized via wet impregnation to systematically evaluate the influence of Ce content on the catalytic performance of NiAl catalysts. The activity results revealed that the optimal 0.5Ce/NiAl catalyst exhibited superior activity (with HFC-134a conversion of 27 %) and remarkable stability (50 h without deactivation). The enhanced performance is attributed to the formation of Ce-O-Al interfacial species. Following fluorination under HF atmosphere, these species evolved into stable Ce-F-Al active centers. Ce-F-Al provides the desired surface acidity for dehydrofluorination of 1,1,1,2-tetrafluoroethane to 1,1,2-trifluoroethylene, as quantitatively demonstrated by NH₃-TPD analysis revealing 885 μmol·g⁻¹ weak and medium acid sites. This tailored acid site distribution simultaneously enhanced catalytic activity and suppressed carbon deposition. Notably, precise control over the abundance of desired acid sites is demonstrated to be a critical factor for achieving both excellent activity and long-term stability in the HFCs-to-HFOs conversion reaction.

将强效温室气体氢氟碳化合物（hfc）转化为高附加值的氢氟烯烃（hfo）非常重要。为了解决转化过程中与强Lewis酸位点相关的碳沉积问题，本研究引入Ce源来修饰NiAl尖晶石的表面酸结构。采用湿浸渍法合成了一系列负载Ce的NiAl氧化物催化剂，系统地考察了Ce含量对NiAl催化剂催化性能的影响。活性结果表明，最佳的0.5Ce/NiAl催化剂具有较好的活性（HFC-134a转化率为27% %）和较好的稳定性（50 h不失活）。性能的增强是由于Ce-O-Al界面物质的形成。在HF气氛下氟化后，这些物种进化成稳定的Ce-F-Al活性中心。Ce-F-Al为1,1,1,2-四氟乙烷脱氢氟化为1,1,2-三氟乙烯提供了所需的表面酸度，NH3-TPD定量分析显示885 μmol·g⁻¹ 弱酸和中酸位点。这种定制的酸位点分布同时增强了催化活性并抑制了碳沉积。值得注意的是，精确控制所需酸位点的丰度被证明是在hfc - hfos转化反应中实现优异活性和长期稳定性的关键因素。

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引用次数: 0

Efficient hydrogen generation via steam reforming of ultra-stable emulsified hydrocarbon fuel catalyzed by NixPt1-x/Al2O3 NixPt1-x/Al2O3催化超稳定乳化烃燃料蒸汽重整高效制氢

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-01-19 DOI: 10.1016/j.apcata.2026.120794

Hongshang Wang , Jingkai Ma , Ruihan Lv , Ji Mi , Wenjun Fang

Traditional steam reforming technology encounters two primary challenges: catalyst deactivation and fuel system instability, which limit its hydrogen production efficiency and potential applications. This work addresses these challenges through the concurrent development of novel catalysts and highly stable fuel emulsions. In this work, ultra-stable quasi-homogeneous “water + JP-10/RP-3” systems were formulated utilizing binary Span 80/Tween 80 emulsifiers. The alloy-structured Ni_0.93Pt_0.07/Al₂O₃ catalyst was synthesized via stirred impregnation followed by annealing. The catalyst demonstrated superior reforming efficiency and resistance to coking: with exo-tetrahydrodicyclopentadiene (JP-10，one of jet fuels) at 740 °C, a gas yield of 28.8 wt% and a hydrogen output of 4.68 mmol·g⁻¹ were achieved alongside a consistent 20 % level of aromatic coke precursors. Furthermore, its capability with complex fuels was affirmed by reforming RP-3 aviation kerosene at 700 °C, which yielded 3.48 mmol·g⁻¹ of H₂. By combining steam reforming performance tests with density functional theory (DFT) calculations, and X-ray absorption fine structure (XAFS) analysis, this study clarifies the dual synergistic effects that contribute to its exceptional performance: (1) Platinum-induced electron-rich nickel significantly decreases the adsorption energy of critical intermediates, hence improving the efficiency of C-H bond activation. (2) The Pt addition markedly diminishes carbon deposition by reducing the tendency of CH_x* intermediates to undergo further dehydrogenation into carbonaceous deposits, facilitating their effective removal.

传统的蒸汽重整技术面临催化剂失活和燃料系统不稳定两大挑战，限制了其制氢效率和应用潜力。这项工作通过同时开发新型催化剂和高度稳定的燃料乳液来解决这些挑战。在这项工作中，超稳定的准均相“水+ JP-10/RP-3”体系采用二元Span 80/Tween 80乳化剂配制。采用搅拌浸渍-退火法制备了合金结构Ni0.93Pt0.07/Al2O3催化剂。该催化剂表现出优异的重整效率和抗焦化性能：在740℃下，以喷气燃料之一的外置四氢二环戊二烯（JP-10）为原料，产气率为28.8 wt%，氢气产量为4.68 mmol·g−1，芳香焦前体含量为20% %。在700℃下对RP-3航空煤油进行重整，得到了3.48 mmol·g−1的H2。本研究通过结合蒸汽重整性能测试和密度泛函理论（DFT）计算，以及x射线吸收精细结构（XAFS）分析，阐明了导致其优异性能的双重协同效应：(1)铂诱导富电子镍显著降低了关键中间体的吸附能，从而提高了C-H键活化效率。(2) Pt的加入降低了CHx*中间体进一步脱氢形成碳质沉积物的倾向，从而显著减少了碳沉积，促进了它们的有效去除。

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引用次数: 0

Exploring the catalytic chan-lam coupling reaction of N-Arylation of amines using heterogeneous thiophene schiff base-Ni-bipy complex on mesoporous MCM-41 利用非均相噻吩席夫碱- ni -bipy配合物在介孔MCM-41上催化n-芳基化反应的研究

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-01-15 DOI: 10.1016/j.apcata.2026.120793

Narmatha Venkatesan, Rajashri Varadarasu, Jayapratha Gunasekaran, Shanmuga Bharathi Kuppannan

The present work is planned to examine the N-arylation of amines using well-defined heterogeneous catalyst. For this process, the mixed thiophene Schiff base and 2,2’-bipyridyl based nickel (II) complex was embedded on hexagonally aligned mesoporous MCM-41 and it has been characterized by the Fourier transform infra-red spectroscopy (FT-IR), powder X-ray diffraction (PXRD), ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), elemental mapping, inductively coupled plasma-optical emission spectrometry (ICP-OES), transmission electron microscope (TEM), thermogravimetric analysis (TGA), N₂ adsorption–desorption isotherm (BET), and X-ray photoelectron spectroscopy (XPS) techniques. The catalytic efficiency of the compound was assessed in N-arylation of amines using phenylboronic acid with various substituted amines (viz. electron donating/ withdrawing, fused ring, heterocyclic and aliphatic substituents), K₂CO₃ under reflux using toluene solvent for 2 h which resulted in excellent yield up to 95 % with independent of their substituents nature. Moreover, hot filtration and recyclability tests of our catalyst validated the heterogeneity nature which worked upto five sequential cycles with maximum stability in the catalytic reaction. A plausible reaction mechanism for the N-arylation of amines and the comparison of catalytic efficiency of our catalyst against some notable reported catalysts were also discussed.

目前的工作是计划检查n -芳基化胺使用明确的异相催化剂。该工艺将噻吩希夫碱和2,2′-联吡啶基镍（II）配合物包埋在六方排列的介孔MCM-41上，并通过傅里叶变换红外光谱（FT-IR）、粉末x射线衍射（PXRD）、紫外-可见漫反射光谱（UV-Vis DRS）、扫描电子显微镜（SEM）、能量色散x射线光谱（EDX）、元素映射、电感耦合等离子体发射光谱（ICP-OES）、透射电子显微镜（TEM）、热重分析（TGA）、N2吸附-脱附等温线（BET）和x射线光电子能谱（XPS）技术。用苯硼酸对不同取代胺（即供电子/吸电子、融合环、杂环和脂肪取代基）、K2CO3在甲苯溶剂回流2 h下进行n -芳基化反应，评价了该化合物的催化效率，收率高达95% %，与取代基性质无关。此外，我们的催化剂的热过滤和可回收性测试验证了非均质性，在催化反应中工作了长达五个连续循环，并具有最大的稳定性。讨论了n -芳基化反应的可能机理，并与已有报道的几种催化剂进行了催化效率的比较。

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引用次数: 0

Aluminum-promoted Co2C-based catalysts for enhanced Fischer-Tropsch synthesis to olefins 铝促进co2c基催化剂促进费托合成烯烃

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-01-14 DOI: 10.1016/j.apcata.2026.120792

Shan Qiao , Kaidi Liu , Xuan Zhou , Ranqing Zhang , Yunlei An , Tiejun Lin , Liangshu Zhong

The promotional effect of aluminum (Al) on Co₂C-based Fischer-Tropsch to olefins (FTO) was systematically investigated. By effectively suppressing methane formation and inhibiting the secondary hydrogenation of olefins, the introduction of Al led to a significant enhancement in olefins production, and the highest selectivity of olefins was achieved at a Co: Mn: Al molar ratio of 3:1:1. Besides, the catalyst stability was also significantly improved with the addition of Al. Structural characterization revealed that Al not only accelerates the carbonization rate of cobalt and reduces the formation of metallic Co⁰, thereby promoting the rapid formation of Co₂C nanoprisms, but also increases the relative content of Co₂C. This modulation enhances the utilization efficiency of cobalt atoms. Notably, the Al promoter also effectively reduced the size of Co₂C nanoparticles from 20.3 to 8.4 nm. This size reduction increased the availability of active sites for syngas conversion to olefins, which was correlated with lower methane selectivity and higher olefins selectivity, as well as improved catalytic stability during syngas conversion. This study presents a simple and effective strategy for optimizing catalytic performance, and provides insights for the rational design of efficient Co₂C-based FTO catalysts.

系统研究了铝（Al）对co2c基费托合成烯烃（FTO）的促进作用。Al的引入有效地抑制了甲烷的生成和烯烃的二次加氢反应，显著提高了烯烃的产量，且在Co: Mn: Al摩尔比为3:1:1时，烯烃的选择性最高。此外，Al的加入也显著提高了催化剂的稳定性。结构表征表明，Al不仅加速了钴的碳化速率，减少了金属Co0的形成，从而促进了Co2C纳米片的快速形成，而且还增加了Co2C的相对含量。这种调制提高了钴原子的利用效率。值得注意的是，Al启动子还有效地将Co2C纳米颗粒的尺寸从20.3 nm减小到8.4 nm。这种尺寸的减小增加了合成气转化为烯烃的活性位点的可用性，这与较低的甲烷选择性和较高的烯烃选择性以及合成气转化过程中催化稳定性的提高有关。本研究提出了一种简单有效的优化催化性能的策略，为合理设计高效的co2c基FTO催化剂提供了参考。

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引用次数: 0

Cerium-doped medium-entropy layered double hydroxides with abundant oxygen vacancies for efficient peroxymonosulfate activation in water purification 具有丰富氧空位的铈掺杂中熵层状双氢氧化物在水净化中的高效过氧单硫酸盐活化

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-01-11 DOI: 10.1016/j.apcata.2026.120790

ZeYi Ren , Hui Bai , Lingyun Fang , XiaoMei Ma , Beibei Sun , Yujie Zhang , Fengqin Tang , JunYi Chen

The rational design of efficient heterogeneous catalysts for peroxymonosulfate (PMS) activation is of great significance for advanced oxidation processes in environmental remediation. Herein, daisy-like quaternary medium-entropy layered double hydroxides (Ce_0.4-MeLDHs) were synthesized via strategic cerium incorporation into the NiCoFe-LDH framework. Ce doping effectively enriched oxygen vacancies and modulated the electronic structure, thereby boosting PMS uptake and activation. Under optimal conditions (pH = 7, PMS =100 mg/L, catalyst = 100 mg/L), Ce_0.4-MeLDHs achieved 96.6 % removal of methylene blue (MB, 20 mg/L) within 12 min, with a reaction rate constant 1.4-fold higher than pristine NiCoFe-LDH. Radical scavenging and electron paramagnetic resonance analyses revealed that ¹O₂ dominated MB degradation, with •OH and •O^–₂ providing synergistic contributions. The superior catalytic activity was ascribed to the interplay between Ce³⁺/Ce⁴⁺ redox cycling, transition-metal redox couples (Ni²⁺/Ni³⁺, Co²⁺/Co³⁺, Fe²⁺/Fe³⁺), and abundant oxygen vacancies (OVs). Furthermore, Ce_0.4-MeLDHs exhibited excellent stability, maintaining > 90 % efficiency after four cycles, and broad-spectrum activity in real water matrices. This work highlights rare-earth doping as an effective strategy to construct entropy-stabilized, oxygen-vacancy-rich LDHs with great promise for sustainable water purification.

合理设计高效的多相催化剂活化过氧单硫酸盐（PMS），对环境修复中高级氧化工艺具有重要意义。本文通过在NiCoFe-LDH框架中加入铈，合成了雏菊状四元介质熵层状双氢氧化物（Ce0.4-MeLDHs）。Ce掺杂有效地富集了氧空位并调节了电子结构，从而促进了PMS的摄取和活化。在最佳条件（pH = 7, PMS =100 mg/L，催化剂=100 mg/L）下，Ce0.4-MeLDHs在12 min内对亚甲基蓝（MB, 20 mg/L）的去除率达到96.6% %，反应速率常数比原始NiCoFe-LDH高1.4倍。自由基清除和电子顺磁共振分析表明，1O2对MB的降解起主导作用，•OH和•O-2起协同作用。Ce3+/Ce4+氧化还原循环、过渡金属氧化还原对（Ni2+/Ni3+、Co2+/Co3+、Fe2+/Fe3+）和丰富的氧空位（OVs）之间的相互作用使其具有优异的催化活性。此外，Ce0.4-MeLDHs表现出优异的稳定性，在四个循环后保持>； 90 %的效率，并在实际水基质中具有广谱活性。这项工作强调稀土掺杂是一种有效的策略，可以构建熵稳定，富氧空位的ldh，具有可持续水净化的巨大前景。

{"title":"Cerium-doped medium-entropy layered double hydroxides with abundant oxygen vacancies for efficient peroxymonosulfate activation in water purification","authors":"ZeYi Ren , Hui Bai , Lingyun Fang , XiaoMei Ma , Beibei Sun , Yujie Zhang , Fengqin Tang , JunYi Chen","doi":"10.1016/j.apcata.2026.120790","DOIUrl":"10.1016/j.apcata.2026.120790","url":null,"abstract":"<div><div>The rational design of efficient heterogeneous catalysts for peroxymonosulfate (PMS) activation is of great significance for advanced oxidation processes in environmental remediation. Herein, daisy-like quaternary medium-entropy layered double hydroxides (Ce<sub>0.4</sub>-MeLDHs) were synthesized via strategic cerium incorporation into the NiCoFe-LDH framework. Ce doping effectively enriched oxygen vacancies and modulated the electronic structure, thereby boosting PMS uptake and activation. Under optimal conditions (pH = 7, PMS =100 mg/L, catalyst = 100 mg/L), Ce<sub>0.4</sub>-MeLDHs achieved 96.6 % removal of methylene blue (MB, 20 mg/L) within 12 min, with a reaction rate constant 1.4-fold higher than pristine NiCoFe-LDH. Radical scavenging and electron paramagnetic resonance analyses revealed that <sup>1</sup>O<sub>2</sub> dominated MB degradation, with •OH and •O<sup>–</sup><sub>2</sub> providing synergistic contributions. The superior catalytic activity was ascribed to the interplay between Ce<sup>3+</sup>/Ce<sup>4+</sup> redox cycling, transition-metal redox couples (Ni<sup>2+</sup>/Ni<sup>3+</sup>, Co<sup>2+</sup>/Co<sup>3+</sup>, Fe<sup>2+</sup>/Fe<sup>3+</sup>), and abundant oxygen vacancies (OVs). Furthermore, Ce<sub>0.4</sub>-MeLDHs exhibited excellent stability, maintaining > 90 % efficiency after four cycles, and broad-spectrum activity in real water matrices. This work highlights rare-earth doping as an effective strategy to construct entropy-stabilized, oxygen-vacancy-rich LDHs with great promise for sustainable water purification.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"712 ","pages":"Article 120790"},"PeriodicalIF":4.8,"publicationDate":"2026-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145974114","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Tailoring support defects in Ru/yttria–ceria catalysts for efficient and durable ammonia decomposition 调整Ru/ ytria - ceria催化剂的支持缺陷，以实现高效和持久的氨分解

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-01-11 DOI: 10.1016/j.apcata.2026.120791

Young Woo Kim , Eun-Jeong Kim , Sungjoon Kweon , Ho Jin Lee , Min Bum Park , Eun Duck Park , Chae-Ho Shin , Yongju Yun

The catalytic decomposition of ammonia (NH₃) offers a carbon-free route for on-demand hydrogen production; however, achieving high activity and durability under moderate temperatures remains challenging. Ru-based catalysts supported on CeO₂ exhibit excellent intrinsic activity, but their performance is limited by insufficient defect density and moderate metal–support interaction. Here, we establish a structure–defect–interaction–performance relationship for Ru catalysts supported on yttria–ceria mixed oxides (Ru/aY-CeO_x) by systematically varying the Y content of the support. Incorporating Y³⁺ into the CeO₂ lattice induces lattice distortion and oxygen vacancies while preserving the fluorite structure up to moderate Y contents. These structural defects strengthen the Ru–O–Ce interfacial bonding, facilitate electron transfer, and enhance the surface basicity of the support. The Ru/50Y-CeO_x catalyst achieves 80 % NH₃ conversion at 450 °C with a hydrogen formation rate of 10.8 mmol∙g_cat⁻¹∙min⁻¹ and maintains stable operation for 168 h without deactivation. This superior performance is attributed to the optimal defect density that maximizes Ru–support coupling, accelerates recombinative N₂ desorption, and mitigates H₂ poisoning. These findings highlight that tailoring lattice defects in rare-earth oxide supports provides a rational strategy for designing efficient and durable Ru-based catalysts for carbon-free hydrogen production.

氨（NH3）的催化分解为按需制氢提供了无碳途径；然而，在中等温度下实现高活性和耐久性仍然具有挑战性。CeO2负载钌基催化剂表现出优异的本禀活性，但缺陷密度不足、金属-载体相互作用不强等因素限制了其性能。在这里，我们通过系统地改变载体的Y含量，建立了钇-铈混合氧化物（Ru/aY-CeOx）负载的Ru催化剂的结构-缺陷-相互作用-性能关系。将Y3+加入到CeO2晶格中会引起晶格畸变和氧空位，同时在Y含量适中的情况下保持萤石结构。这些结构缺陷加强了Ru-O-Ce界面键合，促进了电子转移，提高了载体的表面碱性。在450℃条件下，Ru/50Y-CeOx催化剂NH3转化率达到80 %，制氢速率为10.8 mmol∙gcat−1∙min−1，稳定运行168 h而不失活。这种优异的性能归因于最佳缺陷密度，最大限度地提高了Ru-support耦合，加速了重组N2解吸，减轻了H2中毒。这些发现强调，在稀土氧化物载体中剪裁晶格缺陷为设计高效耐用的无碳制氢钌基催化剂提供了一种合理的策略。

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引用次数: 0

Synthesis and investigation of Cu-containing catalysts based on spherical γ-Al2O3 strengthened with magnesium for deep oxidation in a fluidized bed 含cu球形γ-Al2O3镁强化流化床深度氧化催化剂的合成与研究

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-01-10 DOI: 10.1016/j.apcata.2026.120789

A.P. Lyulyukin, Yu.V. Dubinin, V.A. Yakovlev

This work presents the synthesis and comprehensive investigation of chromium-free catalysts based on γ-Al₂O₃, modified with magnesium oxide (MgO) and copper oxide (CuO), intended for application in thermocatalytic fuel combustion processes under fluidized bed conditions. The preparation technology was optimized by selecting impregnation time, drying, and calcination conditions. X-ray phase analysis confirmed the formation of a spinel solid solution structure Mg_xAl_3-xO₄, which contributes to the strengthening of the carrier. Subsequent introduction of CuO into the strengthened carrier in amounts of 2–5 wt% significantly enhanced catalytic activity, reducing the temperature for achieving 50 % CO conversion to levels comparable with the industrial deep oxidation catalyst DOC. Under vibro-fluidized bed conditions and during combustion of real sewage sludge, the developed catalysts demonstrated a high burnout degree (96–97 %) and low emissions of harmful substances (CO, NO_x, CH₄), comparable to industrial analogs. The obtained results indicate the promise of the proposed approach for the development of effective and environmentally safe catalysts for fuel combustion in fluidized bed.

本文介绍了以氧化镁（MgO）和氧化铜（CuO）改性的γ-Al2O3为基础的无铬催化剂的合成和综合研究，旨在应用于流化床热催化燃料燃烧过程。通过选择浸渍时间、干燥条件和煅烧条件，对制备工艺进行了优化。x射线相分析证实了MgxAl3-xO4尖晶石固溶结构的形成，有利于载体的强化。随后在强化载体中加入2-5 wt%的CuO，显著提高了催化活性，降低了达到50% % CO转化率的温度，达到与工业深度氧化催化剂DOC相当的水平。在振动流化床条件下和真实污泥的燃烧过程中，所开发的催化剂表现出高燃烬度（96 - 97% %）和低有害物质（CO, NOx, CH4）排放，与工业类似物相当。所获得的结果表明，所提出的方法有望开发有效的、环境安全的流化床燃料燃烧催化剂。

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引用次数: 0

Tailored acidity of silylated Pt/USY catalysts to regulate catalytic performances for phenol hydrogenation 硅基化Pt/USY催化剂的酸度调节苯酚加氢催化性能

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-01-09 DOI: 10.1016/j.apcata.2026.120787

Zhi Wang, Jun Chen, Gaolei Shi, Liuwei Shen, Xueqin Ma, Xingguang Zhang

Pt-based catalysts supported on acidic zeolites are intensively utilized for selective hydrogenation reactions; yet the interplay between zeolite acidity and metal sites remains important research topics, because zeolites feature adjustable acidity (Brønsted/Lewis), strong (hydrothermal-)stability, and highly-ordered porosity for nanoconfinement and shape selectivity. This study systematically identifies the contribution of Brønsted (B) acids and Lewis (L) acid sites in Pt/USY catalysts tailored by controlled introduction of diethoxydimethylsilane (DEDMS, 0–5.0 % wt) for phenol hydrogenation to cyclohexanol and cyclohexanone. The modification declined B acid sites (from 145.8 over 1 %Pt/USY-1–14.7 μmol/g over 1 %Pt/5.0 %DEDMS-USY) and L acid sites (from 129.3 to 38.4 μmol/g). The reduction in B acid sites considerably suppressed phenol adsorption and thus decreased its conversion from 100 % (1 %Pt/USY-1) to 19.0 % (1 %Pt/5.0 %DEDMS-USY-1), and the reduction in L acid sites primarily suppressed the cyclohexanone adsorption and thus increased its selectivity from being undetectable (1 %Pt/USY-1) to 57.7 % (1 %Pt/5.0 %DEDMS-USY). The silylation could effectively tailor the catalytic activity and selectivity of Pt/USY catalysts and provides valuable insights for designing bifunctional catalysts in selective hydrogenation.

酸性沸石负载的pt基催化剂被广泛用于选择性加氢反应；然而，沸石酸性和金属位之间的相互作用仍然是重要的研究课题，因为沸石具有可调节的酸度（Brønsted/Lewis），强（热液）稳定性，以及高度有序的孔隙度，用于纳米限制和形状选择性。本研究系统地确定了Brønsted (B)酸和Lewis (L)酸位点在Pt/USY催化剂中的作用，这些催化剂通过控制引入二氧基二甲基硅烷（DEDMS, 0-5.0 % wt）来定制苯酚加氢成环己醇和环己酮。B酸位点（从145.8 μmol/g增加到1 %Pt/ USY-1-14.7 μmol/g增加到1 %Pt/5.0 %DEDMS-USY）和L酸位点（从129.3 μmol/g减少到38.4 μmol/g）。减少B酸网站大大抑制酚吸附,从而降低其转换从100年 %(1 % Pt / USY-1) 19.0 %(1 % Pt / 5.0 % DEDMS-USY-1),和L酸的减少网站主要抑制环己酮的吸附,从而提高了选择性的检测不到(1 % Pt / USY-1) 57.7 %(1 % Pt / 5.0 % DEDMS-USY)。硅基化可以有效地调整Pt/USY催化剂的催化活性和选择性，为设计选择性加氢双功能催化剂提供了有价值的见解。

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引用次数: 0

Zeolite-integrated Brønsted acidity and metal sites for boosted hydrogen generation from ammonia borane methanolysis 沸石集成Brønsted酸性和金属位点，促进氨硼烷甲醇分解制氢

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-01-09 DOI: 10.1016/j.apcata.2026.120788

Yicheng Yu , Shiqi Wang , Tengyue Jiang , Tianjun Zhang , Risheng Bai , Jinhang Dai , Qiming Sun

Hydrogen storage through ammonia borane (AB) methanolysis offers a promising pathway for clean energy systems but is hindered by intrinsic kinetic barriers, necessitating highly efficient catalysts. Here, we report a Ru/SAPO-34 catalyst engineered via a seed-assisted hydrothermal synthesis coupled with steam treatment, which generates abundant surface P–OH groups and optimizes the Brønsted acidity of zeolite frameworks. These phosphorylated hydroxyl sites serve as robust anchoring centers, stabilizing small Ru nanoparticles (∼2.7 nm) introduced by incipient wetness impregnation. Benefiting from the synergy between ultrasmall Ru species and finely tuned acid sites, the optimized Ru/SP34–0.8s-H₂O catalyst delivers a remarkable hydrogen generation rate of 430.1 min^–1 at 298 K and maintains excellent stability over ten successive cycles, surpassing most state-of-the-art catalysts. Kinetic isotope effect analyses further reveal that framework Brønsted acid sites are crucial for O–H bond activation in methanol, thereby accelerating the rate-determining step. This work not only elucidates the mechanistic role of zeolite acidity in AB methanolysis but also establishes a rational design principle for acid–metal cooperative catalysts in chemical hydrogen storage applications.

氨硼烷（AB）甲醇分解储氢为清洁能源系统提供了一条很有前途的途径，但由于内在的动力学障碍，需要高效的催化剂。本文报道了一种Ru/SAPO-34催化剂，该催化剂通过种子辅助水热合成和蒸汽处理，生成了丰富的表面P-OH基团，并优化了沸石骨架的Brønsted酸度。这些磷酸化的羟基位点作为坚固的锚定中心，稳定由初始湿浸渍引入的小Ru纳米颗粒（~ 2.7 nm）。得益于超小Ru物种和精细调节的酸位点之间的协同作用，优化后的Ru/ SP34-0.8s-H2O催化剂在298 K下的产氢速率为430.1 min-1，并且在连续10次循环中保持优异的稳定性，超过了大多数最先进的催化剂。动力学同位素效应分析进一步表明，框架Brønsted酸位点对甲醇中O-H键的激活至关重要，从而加快了速率决定步骤。这项工作不仅阐明了沸石酸性在AB甲醇分解中的机理作用，而且为化学储氢应用中酸-金属协同催化剂的合理设计原则奠定了基础。

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