Applied Catalysis A: General最新文献_第10页

Tailoring Pt valence states in TiO2 thin-film photocatalysts for efficient and durable ammonia-to-N2 conversion 调整TiO2薄膜光催化剂中的Pt价态以实现高效和持久的氨到n2转化

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-10-04 DOI: 10.1016/j.apcata.2025.120621

Min Gie Jung , Ji Eun Seo , Ji Hun Lee , Sung Chang Hong , Dong Wook Kwon

A platinum-loaded TiO₂ thin-film photocatalyst was synthesized via the sol–gel method and applied for the selective catalytic oxidation (photo-SCO) of ammonia to nitrogen under UV irradiation. The catalytic performance was strongly influenced by both the Ti content in the sol and the Pt incorporation method. Increasing Ti loading enhanced the formation of the anatase phase, which promoted higher photocatalytic activity. Two Pt deposition methods were evaluated: UV-assisted photodeposition (M1) and direct addition into the TiO₂ sol (M2). Among these, the M2 method enabled precise control of Pt loading, simplified the preparation process, and significantly reduced the amount of Pt required while maintaining excellent N₂ selectivity. The catalytic activity and durability were further optimized through thermal treatment in various atmospheres. A 50 vol% O₂ atmosphere promoted the formation of higher-valent Pt species, which were positively correlated with NH₃ removal efficiency, N₂ yield, and long-term stability. The Pt-Ti catalyst prepared via the M2 route and calcined in 50 vol% O₂ exhibited over 95 % N₂ yield for 100 h, despite using approximately 1/50 the Pt content compared to M1. Mechanistically, Lewis acid sites on the catalyst surface were identified as the active centers for ammonia activation and selective oxidation to nitrogen. In contrast, the generation of Brønsted acid sites during prolonged operation led to catalyst deactivation. These findings demonstrate a rational design strategy for highly efficient and durable photo-SCO catalysts using minimal noble metal content.

采用溶胶-凝胶法制备了负载铂的TiO2薄膜光催化剂，并将其应用于紫外辐射下氨的选择性催化氧化制氮。溶胶中Ti含量和Pt掺入方式对催化性能均有较大影响。钛负载的增加促进了锐钛矿相的形成，提高了光催化活性。考察了两种铂沉积方法：紫外辅助光沉积（M1）和直接加入TiO2溶胶（M2）。其中，M2法可以精确控制Pt的负载，简化了制备过程，在保持良好的N2选择性的同时显著减少了Pt的用量。通过不同气氛下的热处理，进一步优化了催化剂的催化活性和耐久性。在50 vol% O2气氛下，可促进高价Pt物质的形成，并与NH3去除率、N2产率和长期稳定性呈正相关。通过M2路线制备的Pt- ti催化剂，在50 vol% O2中煅烧100 h，尽管Pt含量约为M1的1/50，但N2产率超过95 %。在机理上，催化剂表面的Lewis酸位点被确定为氨活化和选择性氧化成氮的活性中心。相反，在长时间的操作过程中，Brønsted酸位点的产生导致催化剂失活。这些发现证明了一个合理的设计策略，高效和耐用的光sco催化剂使用最少的贵金属含量。

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引用次数: 0

In situ generation of Ni particles from CaTi1-xNixO3 perovskites used in CO2 methanation 二氧化碳甲烷化用CaTi1-xNixO3钙钛矿原位生成Ni颗粒

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-10-03 DOI: 10.1016/j.apcata.2025.120622

Julio C. Pedrozo Alfonso , Flavia G. Duran , Luis E. Cadús , Octavio J. Furlong , Marcelo S. Nazzarro , Ana M. Beltrán , Gisela M. Arzac , Asunción Fernández , Fabiola N. Aguero

Ni nanoparticles were successfully generated from a CaTi_1-xNi_xO₃ perovskite structure and the effect of Ni substitution level, in the physicochemical characteristics and hence in its catalytic activity and stability in CO₂ methanation reaction was evaluated. Particles were generated by a reduction process, where Ni particles were exsolved to perovskite surface. The samples were characterized by SBET, XRD, XPS, TPR, O₂-TPD, CO₂-TPD, H₂-chemisorption and STEM techniques. CaTi_1-xNi_xO₃ perovskites with high Ni substitution level (x = 2 and 3) presented the highest catalytic performance with almost 90 % CH₄ selectivity and 65 % CO₂ conversion with a low CO selectivity of 3 %. These results could be associated with a higher content of medium basic sites and a higher amount of oxygen vacancies. It was also demonstrated that the exsolution process from a perovskite structure leads to smaller Ni particles than that obtained by the impregnation method. The CaTi_0.7Ni_0.3O₃ catalyst presented good stability during 10 h on time on stream. The stability of the catalyst could be associated with the absence of Ni particle sintering. These results evidenced the potential of these catalysts in the CO₂ methanation process.

采用CaTi1-xNixO3钙钛矿结构制备了镍纳米颗粒，并评价了镍取代水平对CaTi1-xNixO3钙钛矿结构在CO2甲烷化反应中催化活性和稳定性的影响。通过还原过程生成颗粒，镍颗粒在钙钛矿表面析出。采用SBET、XRD、XPS、TPR、O2-TPD、CO2-TPD、h2 -化学吸附和STEM技术对样品进行表征。具有高Ni取代水平（x = 2和3）的CaTi1-xNixO3钙钛矿表现出最高的催化性能，CH4选择性接近90 %，CO2转化率为65 %，CO选择性较低，为3 %。这些结果可能与较高的中基位含量和较高的氧空位量有关。研究还表明，钙钛矿结构的析出过程比浸渍法得到的Ni颗粒更小。CaTi0.7Ni0.3O3催化剂在10 h的上线时间内表现出良好的稳定性。催化剂的稳定性可能与没有Ni颗粒烧结有关。这些结果证明了这些催化剂在二氧化碳甲烷化过程中的潜力。

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引用次数: 0

Development of alumina-supported hydrotalcite-derived CuMgFe catalysts for efficient hydrocarbon synthesis via CO2 hydrogenation 氧化铝负载型水滑石衍生CuMgFe催化剂的研制

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-10-03 DOI: 10.1016/j.apcata.2025.120614

Kentaro Kimura , Ken Nakamura , Jeraldine Docil Calangi , Teruoki Tago

Fischer–Tropsch synthesis via CO₂ hydrogenation represents a promising route for the direct conversion of CO₂ into value-added hydrocarbons, contributing to carbon recycling and sustainable fuel production. In conventional Fe-based catalysts, alkali and alkaline earth metals function as electron promoters for Fe, enhancing Fe carbide formation and thereby facilitating the production of C₂₊ hydrocarbons. Furthermore, transition metals (e.g. Zn, Cu, Mn, Co) enhance carbon chain growth and improve the durability of Fe-based catalysts. This study proposes that abundant interfaces among Cu, Mg, and Fe species are crucial for enhancing CO₂ conversion. An alumina-supported CuMgFe-type hydrotalcite (CuMgFe-HT/Al₂O₃) was developed, yielding highly dispersed metal species that formed ∼5 nm nanoparticles after reduction and providing twice the external surface area of the physical mixture (CuMgFe-HT + Al₂O₃). This catalyst provided a high interface of Cu and other metal oxides, improving CO₂ adsorption. Moreover, the Fe species in CuMgFe-HT/Al₂O₃ exhibited a more electron-rich state than those in impregnated CuMgFe/Al₂O₃, leading to enhanced reducibility of Fe. The CuMgFe-HT/Al₂O₃ achieved a CO₂ conversion of 43 %, with CH₄ selectivity of 23 % and C₅₊ hydrocarbon selectivity of 39 %. In contrast, the impregnated CuMgFe/Al₂O₃ showed higher CH₄ selectivity (35 %) and lower C₅₊ selectivity (24 %). Furthermore, CuMgFe-HT/Al₂O₃ inhibited the sintering of nano-metal particles and exhibited higher catalytic performance with enhanced stability. The interface between Cu and metal oxides (FeO_x and MgO) contributes to the formation and maintenance of Fe carbides, enhancing C–C coupling reactions and providing active sites that can produce C₅₊ hydrocarbons with high stability.

通过二氧化碳加氢的费托合成代表了将二氧化碳直接转化为增值碳氢化合物的有前途的途径，有助于碳循环和可持续燃料生产。在传统的铁基催化剂中，碱金属和碱土金属作为Fe的电子促进剂，促进了Fe碳化物的形成，从而促进了C2+烃的生成。此外，过渡金属（如Zn、Cu、Mn、Co）促进了碳链的生长，提高了铁基催化剂的耐久性。该研究表明Cu、Mg和Fe之间丰富的界面是促进CO2转化的关键。开发了一种氧化铝负载的CuMgFe-HT/Al2O3型水滑石（CuMgFe-HT/Al2O3），生成高度分散的金属物种，还原后形成约5 nm的纳米颗粒，并提供两倍于物理混合物（CuMgFe-HT + Al2O3）的外表面积。该催化剂提供了Cu和其他金属氧化物的高界面，提高了CO2的吸附能力。此外，与浸渍后的CuMgFe- ht /Al2O3相比，CuMgFe- ht /Al2O3中的Fe表现出更富电子的状态，从而增强了Fe的还原性。CuMgFe-HT/Al2O3的CO2转化率为43% %，CH4选择性为23% %，C5+碳氢化合物选择性为39% %。相比之下，浸渍的CuMgFe/Al2O3具有较高的CH4选择性（35 %）和较低的C5+选择性（24 %）。此外，CuMgFe-HT/Al2O3抑制了纳米金属颗粒的烧结，表现出更高的催化性能和增强的稳定性。Cu与金属氧化物（FeOx和MgO）之间的界面有助于Fe碳化物的形成和维持，增强了C-C偶联反应，并提供了活性位点，可以产生高稳定性的C5+碳氢化合物。

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引用次数: 0

Electron acceptor NiO regulates the reduction of Cu supported on TiO2 for the efficient vapor-phase reductive amination of 1, 6-hexanediol 电子受体NiO调节负载在TiO2上的Cu在1,6 -己二醇的高效气相还原胺化反应中的还原

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-10-02 DOI: 10.1016/j.apcata.2025.120615

Haoyu Peng , Zhibin Hu , Yani Liu , Lan Zhou , Pengyu Tang , Liqiu Mao , Wenzhou Zhong , Gouqiang Zou , Dulin yin

The conversion of alcohols recovered from biomass fuel into amine fine chemicals via C-O bond cleavage and C-N bond formation represents a highly desirable approach for amine compound preparation. Hexamethyleneimine (HMI) serves as a pivotal intermediate in the pharmaceutical, agrochemical, and insecticide industries. Industrial HMI production is currently constrained by limited scale and stringent process requirements. This study presents a novel strategy for the selective synthesis of HMI through vapor-phase one-step amination of 1,6-hexanediol (HDO) with ammonia, catalyzed by cost-effective NiO-decorated Cu/TiO₂. Under 1.5 MPa and 215 °C, the NiO-Cu/TiO₂ catalyst achieves complete HDO conversion, with a 98.5 % HMI selectivity and a 1.4-fold enhancement over copper active site alone. Comprehensive characterizations, including XRD, TEM, SEM-EDS, and XPS, elucidate the electronic interactions between copper and nickel oxide that nickel oxide incorporation effectively mitigates charge accumulation on copper, enhancing its hydrogenation capacity and facilitating the conversion of enamine intermediates to imines. DFT calculations reveal that dehydrogenation and hydrogenation processes are rate-determining steps of alcohol amination reaction. This catalyst system, leveraging inexpensive transition metals, holds promise for industrial-scale HMI production via efficient HDO amination.

从生物质燃料中回收的醇通过C-O键裂解和C-N键形成转化为胺类精细化学品是一种非常理想的胺类化合物制备方法。六亚甲基亚胺（HMI）是制药、农用化学品和杀虫剂工业的关键中间体。工业人机界面生产目前受限于有限的规模和严格的工艺要求。本研究提出了一种新的策略，通过低成本的nio修饰Cu/TiO2催化气相一步氨化1,6-己二醇（HDO）选择性合成HMI。在1.5 MPa和215℃条件下，NiO-Cu/TiO2催化剂实现了完全的HDO转化，HMI选择性为98.5% %，比单独使用铜的活性位点提高了1.4倍。通过XRD、TEM、SEM-EDS、XPS等综合表征，揭示了铜与氧化镍之间的电子相互作用，氧化镍的加入有效地减轻了铜的电荷积累，增强了铜的加氢能力，促进了烯胺中间体向亚胺的转化。DFT计算表明，脱氢和加氢过程是醇胺化反应的速率决定步骤。该催化剂系统利用廉价的过渡金属，有望通过高效的HDO胺化实现工业规模的HMI生产。

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引用次数: 0

Rational modulation of d-band centers at graphdiyne/CoGa2O4 heterointerfaces for enhanced visible-light-driven hydrogen evolution 石墨炔/CoGa2O4异质界面d波段中心的合理调制促进可见光驱动析氢

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-10-02 DOI: 10.1016/j.apcata.2025.120619

Shuai Wang , Yihu Ke , Zhiliang Jin

The development of efficient photocatalysts for sustainable hydrogen production is pivotal for addressing global energy and environmental challenges. Herein, we present a novel S-scheme GDY/CoGa₂O₄ heterojunction photocatalyst synthesized via electrostatic self-assembly, engineered to optimize charge dynamics and surface reaction kinetics for enhanced photocatalytic hydrogen evolution. Experimental and theoretical analyses reveal that the built-in electric field at the heterointerface induces an upward shift of the CoGa₂O₄ d-band center toward the Fermi level, balancing hydrogen adsorption/desorption processes and reducing the Gibbs free energy. The synergistic coupling of graphdiyne (GDY)-a two-dimensional carbon allotrope with high conductivity and tunable band structure and spinel-structured CoGa₂O₄ nanoparticles mitigates carrier recombination, extends photogenerated electron lifetimes, and enhances light absorption across 300–800 nm. The hydrogen evolution rate of the optimized GG-30 % composite material reached 156.23 μmol after 5 h, which was 12.24 times and 3.18 times higher than that of the original GDY and CoGa2O4 respectively. while maintaining robust stability over multiple cycles. In situ XPS, KPFM, and transient absorption spectroscopy corroborate efficient S-scheme charge transfer driven by interfacial electric fields, band bending, and Coulomb interactions. This work provides a novel strategy for designing GDY-based photocatalysts through interface engineering.

开发用于可持续制氢的高效光催化剂对于解决全球能源和环境挑战至关重要。在此，我们提出了一种新型的S-scheme GDY/CoGa2O4异质结光催化剂，通过静电自组装合成，优化了电荷动力学和表面反应动力学，以增强光催化析氢。实验和理论分析表明，异质界面处的内置电场诱导CoGa2O4 d带中心向费米能级向上移动，平衡了氢的吸附/解吸过程，降低了吉布斯自由能。石墨二炔（GDY）是一种具有高导电性和可调谐能带结构的二维碳同素异物，它与尖晶石结构的CoGa2O4纳米粒子的协同耦合减轻了载流子的重组，延长了光生电子的寿命，并增强了300-800 nm的光吸收。优化后的GG-30 %复合材料在5 h后的析氢速率达到156.23 μmol，分别是原GDY和CoGa2O4的12.24倍和3.18倍。同时在多个周期中保持强大的稳定性。原位XPS， KPFM和瞬态吸收光谱证实了界面电场，能带弯曲和库仑相互作用驱动的有效S-scheme电荷转移。这项工作为通过界面工程设计基于gdd的光催化剂提供了一种新的策略。

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引用次数: 0

Suppressing N2O formation in Cu-SSZ-13 NH3-SCR by synergistic CeO2/Al2O3 for in situ NO2 management CeO2/Al2O3协同抑制Cu-SSZ-13 NH3-SCR中N2O的生成

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-10-01 DOI: 10.1016/j.apcata.2025.120617

Chunjuan Zhang , Xinyu Li , Wei Li , Xinhua Li , Gurong Shen , Feng Gao , Meiqing Shen

This study addresses the challenge of nitrous oxide (N₂O) emissions in Cu-SSZ-13 based NH₃-SCR systems under Diesel vehicle operating conditions. A bifunctional catalytic system is proposed, integrating CeO₂/Al₂O₃ upstream of Cu-SSZ-13, which reduces N₂O emissions by about 50 % at 150–550 °C with excellent stability. The CeO₂/Al₂O₃ layer dynamically absorbs NO₂ at low temperatures (T < 200 °C) and minimizes the formation of ammonium nitrate, a precursor to N₂O. At higher temperatures, the CeO₂/Al₂O₃ layer promotes the NO₂/NH₃ reaction and again reduces N₂O formation. 0.5–1.0 wt% CeO₂/Al₂O₃ absorbent was found to deliver the best performance, balancing NO₂ absorption capacity and NH₃ oxidation activity. The composite catalyst system demonstrates robust adaptability under various reaction conditions, such as NO₂ concentration and space velocity, and offers a new and viable strategy to enhance NO_x reduction with N₂O suppression for the next-generation SCR technologies.

本研究解决了柴油车工况下基于Cu-SSZ-13的NH3-SCR系统氧化亚氮（N2O）排放的挑战。提出了一种双功能催化体系，在Cu-SSZ-13上游集成CeO2/Al2O3，在150 ~ 550℃范围内，N2O排放量减少约50% %，且稳定性良好。CeO2/Al2O3层在低温（T <； 200°C）下动态吸收NO2，并最大限度地减少硝酸铵的形成，硝酸铵是N2O的前体。在较高温度下，CeO2/Al2O3层促进NO2/NH3反应，再次减少N2O的生成。0.5-1.0 wt% CeO2/Al2O3吸附剂性能最佳，吸附NO2能力和NH3氧化活性达到平衡。该复合催化剂体系对各种反应条件（如NO2浓度和空间速度）具有较强的适应性，为下一代SCR技术提供了一种新的、可行的策略，可以通过抑制N2O来增强NOx的还原。

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引用次数: 0

Photochemistry and homogeneous acid catalysis: A visible light route to β-amino alcohols 光化学和均相酸催化：一种可见光合成β-氨基醇的途径

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-10-01 DOI: 10.1016/j.apcata.2025.120610

Beatrice Bernardoni , Lorenzo Di Terlizzi , Maurizio Fagnoni , Till Bousquet , Stefano Protti

The β-amino alcohol moiety is commonly present in either natural and labmade bioactive compounds with multifaceted applications, spanning pharmaceutics, material sciences and asymmetric synthesis. Among the different strategies adopted to achieve this target, the aminolysis of epoxides in the presence of either Bronsted or Lewis acids is mainly followed. We present herein a versatile, visible light promoted protocol for the preparation of β-amino alcohols from epoxides, by exploiting the peculiar reactivity of photoactivatable arylazo sulfones as Photo Acid Generators (PAGs).

β-氨基醇部分通常存在于天然和实验室制造的生物活性化合物中，具有多方面的应用，包括制药、材料科学和不对称合成。在实现这一目标所采用的不同策略中，主要是在Bronsted酸或Lewis酸的存在下进行环氧化合物的氨解。我们在此提出了一种通用的、可见光促进的方案，利用光活化芳基唑砜作为光酸发生器（PAGs）的特殊反应性，从环氧化物中制备β-氨基醇。

引用次数: 0

Photocatalytic activity of asymmetric cobalt thioporphyrazine for selective aerobic oxidation of amines under visible light 不对称硫卟啉钴在可见光下选择性好氧氧化胺的光催化活性

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-10-01 DOI: 10.1016/j.apcata.2025.120618

Rongjiao Tan, Bingguang Zhang, Xianghong Li, Changjun Yang, Dingguo Tang, Kejian Deng

The development of highly efficient visible-light-driven photocatalysts based on metallothioporphyrazines has recently attracted significant attention for solar energy utilization. In this work, a novel asymmetric cobalt 19,22-bis(butyloxy)-4,5,9,10,14,15-hexakis(butylthio)porphyrazine (denoted as C1) was synthesized through the magnesium template method using 2,3-bis(butylthio)maleonitrile and 3,6-dibutoxyphthalonitrile as precursors. Significantly, the asymmetric C1 exhibited superior photogenerated charge separation capability compared to the symmetric cobalt octakis(butylthio)porphyrazine (denoted as C2), which was testified by photoluminescence spectrum, photocurrent response and electrochemical impedance spectrum. When serving as a visible-light-driven photocatalyst, C1 can selectively oxidize amines to their corresponding imines under visible light (λ ≥ 420 nm) irradiation using atmospheric O₂ as the oxidant, displaying higher photocatalytic activity than C2. Reactive oxygen species including singlet oxygen (¹O₂) and superoxide anion radical (O₂^•-) participated in the photocatalytic oxidation reaction, which were confirmed by active species quenching experiments and electron spin resonance (ESR) measurements. Hammett plot analysis indicated the involvement of a carbocation intermediate in the photocatalytic process. This work provides a new strategy for amine oxidation and highlights the significant potential of asymmetric metallothioporphyrazines as visible-light-driven photocatalysts for organic synthesis.

基于金属硫卟啉的高效可见光驱动光催化剂的开发近年来引起了人们对太阳能利用的极大关注。本文以2,3-二（丁硫）马来腈和3,6-二丁氧基酞腈为前驱体，采用镁模板法合成了新型不对称的19,22-二（丁氧基）-4,5,9,10,14,15-六（丁硫）卟啉嗪（C1）。通过光致发光光谱、光电流响应和电化学阻抗谱分析表明，不对称的C1比对称的octakis（butylthio）卟啉嗪（C2）具有更好的光生电荷分离能力。作为可见光驱动光催化剂时，C1在可见光（λ≥420 nm）照射下，以大气O2为氧化剂，可以选择性地将胺氧化为对应的亚胺，表现出比C2更高的光催化活性。参与光催化氧化反应的活性氧包括单线态氧（1O2）和超氧阴离子自由基（O2•-），通过活性物质猝灭实验和电子自旋共振（ESR）测量得到了证实。Hammett图分析表明碳正离子中间体参与了光催化过程。这项工作为胺氧化提供了一种新的策略，并突出了不对称金属硫卟啉作为有机合成可见光驱动光催化剂的巨大潜力。

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引用次数: 0

NH3 decomposition activity of Ru supported on hydrothermally derived carbon: Temperature effectson the morphological evolution 水热衍生碳负载Ru的NH3分解活性：形态演化中的温度效应

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-10-01 DOI: 10.1016/j.apcata.2025.120616

Miranda Guci , Markus Knäbbeler-Buß , Emma Verkama , Michael Günthel , Md Redwanul Islam , Lorenz Kienle , Erisa Saraçi , Jan-Dierk Grunwaldt , Florian Nestler

A hydrothermally derived carbon support was synthesized from the sustainable feedstock chitosan, with optional subsequent pyrolysis at 600 °C and 1000 °C, to explore its potential as a catalyst support material for ruthenium (Ru). The catalysts were prepared through wet impregnation using Ru nitrosyl nitrate as the precursor. Their catalytic performances in ammonia decomposition were investigated under conditions of 5 % NH₃ at 1 bar, within a temperature range of 300 °C to 600 °C, and a weight hourly space velocity of 15.000 ml_N g_cat⁻¹ h⁻¹. The analytical techniques employed in this study included elemental analysis, thermogravimetric analysis (TGA), gas adsorption measurements, Raman spectroscopy, X-ray diffraction (XRD), flame atomic absorption spectroscopy (F-AAS), scanning transmission electron microscopy (STEM), hydrogen-based temperature-programmed reduction (H₂-TPR) and X-ray photoelectron spectroscopy (XPS). They unraveled that non-pyrolyzed supports showed a strong tendency for Ru agglomeration, whereas pyrolyzed supports exhibited improved metal distribution, which correlated with enhanced catalytic activity exceeding 50 % ammonia conversion at 450 °C. The surface chemistry of the carbon support was modified by varying the pyrolysis temperature, which affected the concentrations and types of oxygen and nitrogen surface groups. These changes altered the interaction between Ru and these surface groups. During the decomposition of the Ru precursor and the reduction of Ru oxides, the partial breakdown of oxygen and nitrogen surface groups led to surface reconstructions of the Ru nanoparticles, thereby affecting their crystallinity. This phenomenon was also observed during the catalytic testing, which was more pronounced on the HC-600 support. Modifying the surface chemistry of hydrochar via pyrolysis affects Ru distribution, reducibility, and crystallinity, thereby enhancing the NH₃ decomposition performance.

以壳聚糖为原料制备了水热衍生碳载体，并在600°C和1000°C下进行了选择性热解，以探索其作为钌（Ru）催化剂载体的潜力。以硝酸亚硝基钌为前驱体，采用湿浸渍法制备催化剂。在5 % NH₃、1 bar、300℃~ 600℃、重量/小时空速15.000 mlN gcat−1 h−1的条件下，研究了它们在氨分解中的催化性能。本研究采用的分析技术包括元素分析、热重分析（TGA）、气体吸附测量、拉曼光谱、x射线衍射（XRD）、火焰原子吸收光谱（F-AAS）、扫描透射电子显微镜（STEM）、氢基程序升温还原（H2-TPR）和x射线光电子能谱（XPS）。他们发现，未热解的载体表现出强烈的Ru团聚倾向，而热解的载体表现出更好的金属分布，这与450°C下超过50% %氨转化率的催化活性增强相关。热解温度的变化改变了碳载体的表面化学性质，影响了氧和氮表面基团的浓度和类型。这些变化改变了钌与这些表面基团之间的相互作用。在Ru前驱体分解和Ru氧化物还原过程中，氧和氮表面基团的部分击穿导致Ru纳米颗粒的表面重构，从而影响其结晶度。在催化试验中也观察到这种现象，在HC-600载体上更为明显。通过热解改性烃类的表面化学性质，可以影响Ru的分布、还原性和结晶度，从而提高NH₃的分解性能。

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引用次数: 0

Impact of adding C2H6 on the CO2 reforming of CH4 over Al-Incorporated Co/MgAl2O4 catalyst 添加C2H6对al - Co/MgAl2O4催化剂上CH4 CO2重整的影响

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-09-30 DOI: 10.1016/j.apcata.2025.120607

Jung-Hyun Park, Hyeryeung Noh, Hwa Sung Lee, Joong Jin Han, Tae-Sun Chang

This study investigates the impact of incorporating aluminum (Al) as a promoter into a Co/MgAl₂O₄ (MA) catalyst for the CO₂ reforming of CH₄ with C₂H₆. The Co/MA catalyst exhibited the highest initial conversion of CH₄ and CO₂; however, both values gradually declined over the time. In contrast, all Al-promoted catalysts maintained stable conversions, and the CoAl(0.50)/MA catalyst demonstrated notable catalytic stability after 50 h of reaction. The weight of the Al-promoted catalyst either remained constant or increased slightly compared with the Al-unpromoted catalyst during CH₄-TGA, indicating superior resistance to coking. Although the exact location of the Al species could not be determined experimentally, it can be inferred that the appropriate addition of Al to the Co/MA catalyst may partially form a CoAl₂O₄ phase, which facilitates CO₂ activation and suppresses carbon deposition. This suggests that the Al promoter kinetically controls the rate of carbon deposition and oxidation on the Co/MA catalyst.

本文研究了在Co/MgAl2O4 （MA）催化剂中加入铝（Al）作为促进剂对C2H6催化CH4的CO2重整反应的影响。Co/MA催化剂对CH4和CO2的初始转化率最高；然而，随着时间的推移，这两个值逐渐下降。相比之下，所有al促进的催化剂都保持稳定的转化率，煤(0.50)/MA催化剂在反应50 h后表现出显著的催化稳定性。在CH4-TGA过程中，与非al促进催化剂相比，al促进催化剂的重量保持不变或略有增加，表明其具有更强的抗结焦性。虽然实验无法确定Al的确切位置，但可以推断，在Co/MA催化剂中适当添加Al可能会部分形成CoAl2O4相，从而促进CO2的活化，抑制碳沉积。这表明Al促进剂在动力学上控制Co/MA催化剂上的碳沉积和氧化速率。

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