Catalysis Today最新文献_第6页

Hierarchical zeolites for dimethyl ether dehydration into light olefins 分级沸石用于二甲醚脱水成轻烯烃

IF 5.3 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2025-10-27 DOI: 10.1016/j.cattod.2025.115618

Fabio Salomone , Giorgia Ferrarelli , Emanuele Giglio , Elena Corrao , Massimo Migliori , Samir Bensaid , Raffaele Pirone , Girolamo Giordano

Dimethyl ether (DME) conversion into light olefins (DTO) is a process that can lead to the sustainable production of molecules like ethylene, propylene, and butenes, which are key building blocks in the chemical industry. Acid catalysts involved in the conversion of methanol and DME into hydrocarbons (MTO and DTO) are usually affected by fast deactivation due to coke generation. In the present study, four hierarchical zeolites were synthesized with different Si/Al ratios according to two procedures: a post-treatment (named “etching”) of a HZSM-5 microporous zeolite with a solution of ammonium fluoride and hydrofluoric acid, and a one-pot bottom-down approach involving an organosilane to induce mesoporosity during the hydrothermal synthesis. The samples were characterized from a physico-chemical standpoint to assess crystallinity, textural properties, and acidity. All the synthesized zeolites were then tested for about 14 h in the DTO process at a temperature range of 300–375 °C. Results showed that hierarchical zeolites with mild acidity have a very good stability, even when they are tested at the highest temperature, at which conventional microporous samples deactivate quickly. Conversion of 80–90 % is achieved at 375 °C and a space velocity of 1 g_cat∙h∙mol_C⁻¹, with propylene as the most abundant product. Samples prepared via one-pot synthesis resulted in a greater propylene-to-ethylene ratio, partly due to shape selectivity related to the pore size distribution.

二甲醚（DME）转化为轻烯烃（DTO）是一个可以导致可持续生产乙烯、丙烯和丁烯等分子的过程，这些分子是化学工业的关键组成部分。参与甲醇和二甲醚转化为烃类（MTO和DTO）的酸性催化剂通常由于生焦而快速失活。在本研究中，采用两种方法合成了4种不同Si/Al比的分级沸石：一种是用氟化铵和氢氟酸溶液对HZSM-5微孔沸石进行后处理（称为“蚀刻”），另一种是在水热合成过程中使用有机硅烷诱导介孔的一锅自下而上的方法。从物理化学的角度对样品进行了表征，以评估结晶度、结构性质和酸度。然后在300-375℃的DTO过程中对所有合成的沸石进行了约14 h的测试。结果表明，即使在常规微孔样品快速失活的最高温度下进行测试，具有温和酸度的分级沸石也具有非常好的稳定性。在375 °C和1 gcat∙h∙molC−1的空速条件下，转化率可达80 - 90%，产物中丙烯含量最多。通过一锅合成制备的样品导致更大的丙烯与乙烯比，部分原因是与孔径分布相关的形状选择性。

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引用次数: 0

Development of highly active Co/Mo2C catalysts for green H2 production from NH3 NH3绿色制氢高效Co/Mo2C催化剂的研制

IF 5.3 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2025-10-24 DOI: 10.1016/j.cattod.2025.115615

M. Pinzón , C. Martín , A. Romero , A. de Lucas-Consuegra , A.R. de la Osa , P. Sánchez

The development of cost-effective catalysts with excellent catalytic performance is of great interest for ammonia cracking. In this work, an innovative and stable cobalt catalyst supported on a commercial molybdenum carbide material was prepared. The influence of pre-activation treatment on the catalytic activity of a 5Co/Mo₂C catalyst for ammonia decomposition was investigated using H₂/Ar and NH₃/Ar at 400 °C. Both activations resulted in a high ammonia conversion (∼ 90 %) at 500 °C. XPS analysis revealed that H₂ pre-activation resulted in greater surface Co/Mo ratio and enhanced charge transfer, contributing to increase active cobalt and hence better catalytic activity. The effect of cobalt loading (2.5–10 wt%) was further optimized, with 7.5Co/Mo₂C achieving the highest conversion (93.7 % at 450 °C), attributed to optimal Co dispersion and crystallite size (∼16.8 nm). The addition of a secondary metal (K, Cs or La) to the 7.5Co/Mo₂C catalyst showed that lanthanum significantly improved the catalytic activity by increasing the basicity, cobalt dispersion, and surface Co/Mo ratio. In contrast, K and Cs had a negative effect, causing agglomeration and reduction of active sites by blocking. These findings indicate that H₂ pre-activation and La promotion were key factors for enhancing ammonia decomposition efficiency on Co/Mo₂C catalyst.

开发具有优异催化性能的低成本催化剂是氨裂化的重要研究方向。在这项工作中，制备了一种创新的、稳定的钴催化剂，负载在商业碳化钼材料上。在400 ℃条件下，以H2/Ar和NH3/Ar为催化剂，研究了预活化处理对5Co/Mo2C催化剂氨分解活性的影响。在500 °C时，两种活化都导致高氨转化率（~ 90 %）。XPS分析表明，H2预活化导致表面Co/Mo比增大，电荷转移增强，从而提高了活性钴，从而提高了催化活性。进一步优化了钴负载（2.5-10 wt%）的效果，在450 °C时，7.5Co/Mo2C的转化率最高（93.7 %），这归功于最佳的Co分散和晶体尺寸（~ 16.8 nm）。在7.5Co/Mo2C催化剂中添加二次金属（K、Cs或La）表明，镧通过提高碱度、钴分散度和表面Co/Mo比显著提高了催化活性。相反，K和Cs则有负面作用，通过阻断导致活性位点聚集和减少。结果表明，H2预活化和La促进是提高Co/Mo2C催化剂上氨分解效率的关键因素。

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引用次数: 0

Selective leaching method for the regeneration of vanadium-contaminated FCC catalysts 钒污染FCC催化剂再生的选择性浸出法

IF 5.3 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2025-10-24 DOI: 10.1016/j.cattod.2025.115616

Deok Woo Kim, Na Yeon Kim, Dong Seop Choi, Jiyull Kim, Ji Bong Joo

Metal contaminant accumulation, particularly vanadium, in fluid catalytic cracking (FCC) catalysts significantly reduces their activity and efficiency. Washing and recycling processes are effective and economical methods for not only removal of metal contaminant but also catalyst regeneration. In this work, we investigated leaching behavior of vanadium species from a simulated spent FCC catalyst by varying leaching agents and compared both characteristics and cracking performances. A simulated spent catalyst was prepared by contaminating the synthesized zeolite-based catalysts with vanadium via wet impregnation under a high-temperature steam environment to mimic regenerator conditions. The resulting contaminated catalyst, VC-FCC, was leached with both acidic (HCl and AcOH) and alkaline (NaOH and NH₃(aq)) solutions. It is investigated that the selective vanadium leaching, and facile catalyst regeneration can be suitable by alkaline solution based leaching method. The NH₃ (aq) leached catalyst exhibited a conversion and gasoline yield up to 2.74 (87.1 %) and 1.37 (25.9 %) times higher, respectively, than other leached catalysts using leaching agents. Thus, NH₃ (aq) leaching is an effective method for regenerating contaminated FCC catalysts, making it suitable for sustainable catalyst management in gasoline production.

金属污染物的积累，特别是钒，在流体催化裂化（FCC）催化剂显著降低其活性和效率。洗涤和回收工艺是一种既能去除金属污染物又能实现催化剂再生的经济有效的方法。在这项工作中，我们研究了不同浸出剂对模拟FCC废催化剂中钒的浸出行为，并比较了两者的特征和裂解性能。在模拟再生条件的高温蒸汽环境下，用钒湿浸渍法对合成的沸石基催化剂进行污染，制备了模拟废催化剂。得到的污染催化剂VC-FCC用酸性（HCl和AcOH）和碱性（NaOH和NH3(aq)）溶液进行浸出。研究了碱液基浸出法可适用于钒的选择性浸出和易催化剂再生。NH3 （aq）浸出催化剂的转化率和汽油收率分别比使用浸出剂的其他浸出催化剂高2.74（87.1 %）和1.37（25.9 %）。因此，NH3 （aq）浸出是一种有效的再生污染催化裂化催化剂的方法，适用于汽油生产中催化剂的可持续管理。

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引用次数: 0

Catalytic enhancement on nanowire-engineered thermally stable oxide-metal inverse catalysts 纳米线工程热稳定氧化物-金属反相催化剂的催化增强

IF 5.3 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2025-10-20 DOI: 10.1016/j.cattod.2025.115612

Gyuho Han , Seongsu Choi , Hee Chan Song , Gyu Rac Lee , Jaebeom Han , Pyeonghwa Lee , Jaeho Kim , Han-Koo Lee , Si Woo Lee , Yeon Sik Jung , Jeong Young Park

The interface between metal and oxide plays a critical role in heterogeneous catalysis. In this study, we fabricated model inverse catalysts by transferring oxide nanowire assemblies of Co₃O₄, CeO₂, and TiO₂ onto Pt films to construct structurally well-defined oxide-metal interfaces. The deposited oxide nanowires retained their morphology without noticeable diffusion or sintering during annealing and carbon monoxide oxidation, as confirmed by near-edge X-ray absorption fine structure analysis. The surface electronic structure and morphology of the Pt film also remained largely unchanged, preserving the oxide-metal interfaces, which exhibited significant enhancements in turnover frequencies, depending on the oxide composition. These results highlight the utility of oxide nanowires in constructing thermally stable and composition-tunable oxide-metal interfaces for catalytic systems.

金属与氧化物之间的界面在非均相催化中起着至关重要的作用。在这项研究中，我们通过将Co3O4， CeO2和TiO2的氧化物纳米线组件转移到Pt薄膜上来构建结构明确的氧化物-金属界面来制备模型反催化剂。近边x射线吸收精细结构分析证实，在退火和一氧化碳氧化过程中，沉积的氧化纳米线没有明显的扩散和烧结。Pt薄膜的表面电子结构和形貌也基本保持不变，保留了氧化物-金属界面，根据氧化物成分的不同，其转换频率显著增强。这些结果突出了氧化物纳米线在为催化系统构建热稳定和成分可调的氧化物-金属界面方面的应用。

引用次数: 0

Enhancing higher alcohols selectivity in CO2 hydrogenation over FeCu catalysts via Mg modification 通过Mg改性提高FeCu催化剂CO2加氢的高醇选择性

IF 5.3 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2025-10-17 DOI: 10.1016/j.cattod.2025.115614

Baojian Chen , Caixia Zhu , Haozhe Feng , Teng Li , Zhihao Liu , Zhenzhou Zhang , Yingluo He , Noritatsu Tsubaki

CO₂ hydrogenation to higher alcohols (C₂₊OH) over FeCu-based catalysts offers a promising route for carbon recycling. However, challenges such as low carbon utilization efficiency and limited product selectivity still exist due to the complexity of the reaction network and unclear formation mechanisms. Herein, a series of Mg-modified FeCu-based catalysts (2Na/Fe₁Cu₂Mg_x) with varying Mg content were synthesized via co-precipitation method, and their catalytic performance of CO₂ hydrogenation to C₂₊OH were investigated. The introduction of an appropriate amount of Mg significantly reduced the particle size of active metals and enhanced the metal-metal interaction between Cu and Fe species, thus further facilitated the formation of a highly dispersed Cu-χ-Fe₅C₂ interface structure. Multiple advanced characterizations have demonstrated that Cu-χ- Fe₅C₂ well-defined interface improved the adsorption capacities for both CO₂ and CO, simultaneously promoting the synergistic coupling of CHₓ and CO intermediates for the highly selective formation of C₂₊OH products. The 2Na/Fe₁Cu₂Mg₁ catalyst achieved a C₂₊OH selectivity of 25.4 % and a space-time yield (STY) of 75.1 mg·g_cat^-¹ ·h^-¹ with CO₂ conversion of 32.6 % under 320 °C, 5.0 MPa. Remarkably, the STY further rose to 110.1 mg·g_cat^-¹ ·h^-¹ when the reaction temperature increased to 380 °C, with a CO₂ conversion reaching 55.4 % and CO selectivity reduced to just 6.7 %. This study elucidates the pivotal role of Mg in modulating catalyst structure and constructing efficient active interfaces, providing a new theoretical foundation and design strategy for the rational development of highly selective catalysts for CO₂ hydrogenation to higher alcohols.

在feu基催化剂上，CO2加氢生成高级醇（C2+OH）为碳循环利用提供了一条很有前途的途径。然而，由于反应网络的复杂性和形成机制的不明确，仍然存在碳利用效率低、产物选择性有限等挑战。本文采用共沉淀法合成了一系列Mg含量不同的Mg改性feu基催化剂（2Na/Fe1Cu2Mgx），并对其催化CO2加氢制C2+OH的性能进行了研究。适量Mg的加入显著减小了活性金属的粒径，增强了Cu和Fe之间的金属-金属相互作用，从而进一步促进了Cu-χ-Fe5C2界面结构的形成。多次高级表征表明，Cu-χ- Fe5C2明确的界面提高了对CO2和CO的吸附能力，同时促进CHₓ和CO中间体的协同耦合，以高选择性地形成C2+OH产物。在320℃，5.0 MPa条件下，2Na/Fe1Cu2Mg1催化剂的C2+OH选择性为25.4 %，空时产率（STY）为75.1 mg·gcat-¹ ·h-¹ ，CO2转化率为32.6% %。值得注意的是，当反应温度提高到380℃时，STY进一步提高到110.1 mg·gcat-¹ ·h-¹ ，CO2转化率达到55.4% %，CO选择性降至6.7 %。本研究阐明了Mg在调节催化剂结构和构建高效活性界面中的关键作用，为合理开发高选择性CO2加氢制高级醇催化剂提供了新的理论基础和设计策略。

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引用次数: 0

Synthesis of ammonia under an electric field using lanthanum-based catalysts 利用镧基催化剂在电场下合成氨

IF 5.3 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2025-10-17 DOI: 10.1016/j.cattod.2025.115613

Aida Younis , Fiza Akbar , Elodie Fourré , André Grishin , Catherine Batiot-Dupeyrat

The use of ammonia as a hydrogen carrier is a fast-growing research area due to ammonia’s high weight percentage of H₂ (17.6 %) and its safer to handle features. Therefore, a higher demand for ammonia in energy applications is expected in the near future. Electric field-assisted ammonia synthesis is one way to meet the growing demand for ammonia, both for energy purposes and for industrial applications, mainly in fertilizer production. This study highlights the use of electric current for ammonia production by using NiO/La₂O₃ catalysts in a fixed-bed flow reactor. The operating conditions were maintained at a pressure of 5 bars and a current of 9 mA. The catalytic activity was analyzed in terms of ammonia concentration (ppm), synthesis rate

R_{{NH}_{3}}

(µmol.min⁻¹.g_cat⁻¹) and energy efficiency EE (g-NH₃ [kWh.g_cat⁻¹]⁻¹). Good catalytic activity was obtained at 200 °C for the 10 wt% NiO/La₂O₃ catalyst, with

R_{{NH}_{3}}

and EE values reaching 5.7 µmol.min⁻¹.g_cat⁻¹ and 4.5 g-NH₃ [kWh.g_cat⁻¹]⁻¹, respectively. Characterization of the catalysts by powder X-Ray Diffraction (XRD) revealed the formation of La(OH)₃ from La₂O₃ in the presence of electric field, and an altered reaction mechanism was observed. The temperature-dependent study showed an increase in NH₃ production at 150 °C and 200 °C with an apparent activation energy of 30 kJ.mol⁻¹.

氨作为氢载体是一个快速发展的研究领域，因为氨的H2重量百分比高（17.6%），而且处理起来更安全。因此，预计在不久的将来，能源应用对氨的需求会更高。电场辅助氨合成是满足日益增长的氨需求的一种方法，既用于能源目的，也用于工业应用，主要用于肥料生产。本研究重点介绍了在固定床流动反应器中使用NiO/La2O3催化剂生产氨的电流。工作条件维持在5 bar的压力和9 mA的电流。以氨浓度（ppm）、合成速率RNH3（µmol.min - 1）为指标分析催化活性。gcat−1)和能效EE （g-NH3 [kWh.gcat−1]−1）。10 wt% NiO/La2O3催化剂在200℃下具有良好的催化活性，thrnh3和EE值达到5.7µmol.min−1。gcat−1和4.5 g-NH3 [kWh]。分别gcat−1)−1。粉末x射线衍射（XRD）表征了催化剂在电场作用下由La2O3生成La(OH)3，并观察了反应机理的变化。温度依赖性研究表明，在150°C和200°C时NH3产量增加，表观活化能为30 kJ.mol−1。

{"title":"Synthesis of ammonia under an electric field using lanthanum-based catalysts","authors":"Aida Younis , Fiza Akbar , Elodie Fourré , André Grishin , Catherine Batiot-Dupeyrat","doi":"10.1016/j.cattod.2025.115613","DOIUrl":"10.1016/j.cattod.2025.115613","url":null,"abstract":"<div><div>The use of ammonia as a hydrogen carrier is a fast-growing research area due to ammonia’s high weight percentage of H2 (17.6 %) and its safer to handle features. Therefore, a higher demand for ammonia in energy applications is expected in the near future. Electric field-assisted ammonia synthesis is one way to meet the growing demand for ammonia, both for energy purposes and for industrial applications, mainly in fertilizer production. This study highlights the use of electric current for ammonia production by using NiO/La2O3 catalysts in a fixed-bed flow reactor. The operating conditions were maintained at a pressure of 5 bars and a current of 9 mA. The catalytic activity was analyzed in terms of ammonia concentration (ppm), synthesis rate <math><msub><mrow><mi>R</mi></mrow><mrow><msub><mrow><mi>NH</mi></mrow><mrow><mn>3</mn></mrow></msub></mrow></msub></math>(µmol.min−1.gcat−1) and energy efficiency EE (g-NH3 [kWh.gcat−1]−1). Good catalytic activity was obtained at 200 °C for the 10 wt% NiO/La2O3 catalyst, with<math><msub><mrow><mi>R</mi></mrow><mrow><msub><mrow><mi>NH</mi></mrow><mrow><mn>3</mn></mrow></msub></mrow></msub></math> and EE values reaching 5.7 µmol.min−1.gcat−1 and 4.5 g-NH3 [kWh.gcat−1]−1, respectively. Characterization of the catalysts by powder X-Ray Diffraction (XRD) revealed the formation of La(OH)3 from La2O3 in the presence of electric field, and an altered reaction mechanism was observed. The temperature-dependent study showed an increase in NH3 production at 150 °C and 200 °C with an apparent activation energy of 30 kJ.mol−1.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"463 ","pages":"Article 115613"},"PeriodicalIF":5.3,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145359565","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

Synthesis of stable Ni catalysts for dry reforming of methane via ABC-type atomic layer deposition abc型原子层沉积法合成甲烷干重整稳定镍催化剂

IF 5.3 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2025-10-16 DOI: 10.1016/j.cattod.2025.115609

Sol Ahn , Tobin J. Marks , Peter C. Stair

Three different precursors were used to synthesize isolated Ni sites as well as to stabilize them on an Al₂O₃ support for the dry reforming of methane (DRM) reaction. The precursors used are bis(cyclopentadienyl)nickel(II) (A cycle), trimethyl aluminum (B cycle), and water (C cycle). This so-called ABC-type atomic layer deposition (ALD) was performed for 15 cycles, and then overcoated with an Al₂O₃ layer via ALD to enhance the stability of the DRM catalyst. Pore morphologies were retained after this ABC-type ALD/calcination/additional Al₂O₃ ALD, confirming the thin film deposition occurs without compromising pore structure of the Al₂O₃ support. Calcination after 15 cycles of ABC-type ALD is required to recover the DRM activity as well as to improve the stability. Overcoating with 5 cycles of Al₂O₃ results in higher peak DRM activity versus the calcined catalyst, but that with 10 cycles does not. Additional Al₂O₃ overcoating changes the deactivation rate constants to a small extent, but results in induction periods indicating the presence of NiAl₂O₄. The catalyst with 5 cycles of Al₂O₃ overcoating shows a higher peak DRM rate than those with 0 and 10 cycles, and a lower deactivation rate constant. These results indicate that achieving an optimum number of ABC cycles may help resolve the trade-off between peak rate and deactivation behavior for Ni DRM catalysts.

用三种不同的前驱体合成了分离的Ni位点，并在Al2O3载体上稳定了它们，用于甲烷干重整（DRM）反应。使用的前体是双（环戊二烯基）镍（II）（A循环）、三甲基铝（B循环）和水（C循环）。这种所谓的abc型原子层沉积（ALD）进行了15次循环，然后通过ALD覆盖了Al2O3层，以提高DRM催化剂的稳定性。在abc型ALD/煅烧/添加Al2O3 ALD后，孔隙形态得以保留，这证实了薄膜沉积在不影响Al2O3载体孔隙结构的情况下发生。abc型ALD经过15个循环后需要煅烧，以恢复DRM活性并提高稳定性。与煅烧催化剂相比，5次Al2O3复涂导致DRM活性峰值更高，但10次循环则没有。额外的Al2O3覆盖层在一定程度上改变了失活速率常数，但导致了诱导期，表明NiAl2O4的存在。Al2O3复涂5次的催化剂的峰值DRM速率高于复涂0次和复涂10次的催化剂，且失活速率常数较低。这些结果表明，获得最佳的ABC循环次数可能有助于解决Ni DRM催化剂的峰值速率和失活行为之间的权衡。

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引用次数: 0

Macroscopic structures based on La0.8Me0.2NiO3±δ (Me = Al, Ba and Ca) perovskites for renewable hydrogen production through thermochemical water splitting 基于La0.8Me0.2NiO3±δ （Me = Al， Ba和Ca）钙钛矿的热化学水裂解再生制氢宏观结构

IF 5.3 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2025-10-16 DOI: 10.1016/j.cattod.2025.115610

Alejandro Pérez , María Orfila , María Linares , Raúl Sanz , Javier Marugán , Raúl Molina , Juan A. Botas

The worrying energy and climate situations make it necessary to face a transition to a carbon-neutral economy. In this context, green hydrogen plays a crucial role in the future energy landscape. Besides other technologies, thermochemical water splitting represents a promising route for renewable hydrogen generation, using thermosolar energy as the primary energy source. In this study, different types of perovskites La_0.8Me_0.2NiO_3±δ (Me = Al, Ba and Ca) were synthesised via reactive grinding. Their redox performance was evaluated under different thermal reduction temperatures (1200–800 °C), obtaining materials with hydrogen production values ranging from 4.51 to 5.31 cm³STP/g_{active material}·cycle when the reduction was performed at 800 °C, exceeding those already reported values for similar materials at higher temperatures. In order to obtain suitable configurations for their implementation in solar reactors, powdered perovskites were shaped into macrostructures such as pellets, reticulated porous ceramic (RPC) structures and thin films deposited over ceramic monoliths. Compared to powdered materials, the macrostructures exhibited higher hydrogen production attributed to enhanced gas-solid contact and more efficient heat transfer within the structures. The best performance was obtained by La_0.8Ca_0.2NiO_3±δ supported as a thin layer over the ceramic monolithic structure, with productions up to 14.91–16.33 cm³STP/g_{active material}·cycle using thermal reduction temperatures of 800 and 1000 °C, respectively. These results confirm that shaping strategies enhance the already remarkable redox activity of perovskites and enable their integration into volumetric solar reactors. This represents a significant step forward in the development of scalable green hydrogen production systems based on renewable solar thermal energy.

令人担忧的能源和气候形势使我们有必要向碳中和经济转型。在这种背景下，绿色氢在未来的能源格局中扮演着至关重要的角色。除了其他技术外，热化学水裂解是一种有前途的可再生制氢途径，使用太阳能作为主要能源。本研究采用反应研磨法合成了不同类型的钙钛矿La0.8Me0.2NiO3±δ （Me = Al， Ba和Ca）。在不同的热还原温度（1200-800°C）下评估了它们的氧化还原性能，当在800 °C下进行还原时，得到的材料的产氢值为4.51至5.31 cm³STP/活性物质·循环，超过了已经报道的类似材料在更高温度下的值。为了在太阳能反应器中获得合适的结构，粉末钙钛矿被塑造成宏观结构，如颗粒、网状多孔陶瓷（RPC）结构和沉积在陶瓷单体上的薄膜。与粉状材料相比，由于增强的气固接触和结构内更有效的传热，宏观结构表现出更高的产氢率。La0.8Ca0.2NiO3±δ作为薄层支撑在陶瓷单片结构上获得了最好的性能，热还原温度分别为800和1000 °C时，产量可达14.91 ~ 16.33 cm³STP/活性材料·循环。这些结果证实，成型策略增强了钙钛矿已经显著的氧化还原活性，并使其能够集成到体积太阳能反应器中。这代表了基于可再生太阳能热能的可扩展绿色制氢系统的发展向前迈出的重要一步。

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引用次数: 0

Breaking the linear scaling relationship in CO2 reduction by p-block doping at Au(332) surface 在Au（332）表面p-嵌段掺杂破坏CO2还原中的线性标度关系

IF 5.3 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2025-10-14 DOI: 10.1016/j.cattod.2025.115607

Hanna Jeon , Hyeonwoo Kim , Jonghun Lim , Hyeyoung Shin

Breaking the linear scaling relationship (LSR) between COOH and CO adsorption remains a key challenge in designing efficient electrocatalysts for the CO₂ reduction reaction (CO₂RR). Here, density functional theory calculations show that doping p-block elements into the step sites of Au(332) selectively stabilizes the COOH intermediate, thereby breaking the intrinsic LSR. Among 20 screened p-block elements, Si emerges as the most promising dopant. It strongly stabilizes COOH and consequently shifts the rate-determining step, ultimately lowering the overpotential. Electronic structure analyses reveal that the localized p_z orbital of Si engages in covalent interactions with the radical-like COOH, while interacting only weakly with the closed-shell CO. This orbital-specific decoupling enables independent tuning of intermediate adsorption energies. These findings establish p-block doping as a viable strategy to overcome the fundamental limitations of transition metal surfaces in CO₂RR, and provide a rational design principle for next-generation catalytic materials.

打破COOH与CO吸附之间的线性结垢关系（LSR）是设计高效CO2还原反应（CO2RR）电催化剂的关键挑战。这里，密度泛函理论计算表明，在Au（332）的阶位中掺杂p-嵌段元素选择性地稳定了COOH中间体，从而打破了本然LSR。在筛选的20种p块元素中，Si是最有前途的掺杂剂。它强有力地稳定了COOH，从而改变了速率决定步骤，最终降低了过电位。电子结构分析表明，Si的定域pz轨道与类自由基COOH发生共价相互作用，而与封闭壳层CO的相互作用较弱。这种轨道特异性解耦使得中间吸附能能够独立调节。这些发现为克服CO2RR中过渡金属表面的基本限制提供了可行的策略，并为下一代催化材料的设计提供了合理的原则。

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引用次数: 0

Hierarchical regression approach for enhanced performance prediction of ammonia decomposition catalysts 氨分解催化剂强化性能预测的层次回归方法

IF 5.3 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2025-10-14 DOI: 10.1016/j.cattod.2025.115608

Jisu Park , Jaeseok An , Sujin Kim, Yongju Yun

Enhancing the accuracy of predictive models for catalytic performance is critical for effectively leveraging accumulated data and optimizing catalysts and operating conditions. This study evaluates the potential of hierarchical regression models in predicting the hydrogen formation rate during ammonia decomposition at elevated reaction temperatures. Using a literature database, we trained sequential, random, and inverse hierarchical regression models, alongside non-hierarchical models, on data collected at lower temperatures. A comparison of predictive accuracies revealed that the sequential hierarchical models, organized by increasing temperature, provided the highest accuracy. This finding illustrates the model’s capability to capture the nonlinear relationship between reaction temperature and catalytic performance. In contrast, both random and inverse hierarchical models performed worse than non-hierarchical models, highlighting the importance of subset training order on hierarchical model performance. Examining the effects of subset configuration, hierarchy level, and algorithm type on the predictive accuracy of sequential hierarchical models for ammonia decomposition provides insight into the optimized design of these models. The successful application of hierarchical regression models in the prediction of catalytic performance demonstrates their advantages in capturing the complexity inherent in the heterogeneous catalysis database. Ultimately, the hierarchical model shows strong potential for robust and generalizable predictions under various reaction temperatures in ammonia decomposition, extending beyond the original training domain.

提高催化性能预测模型的准确性对于有效利用积累的数据和优化催化剂和操作条件至关重要。本研究评估了层次回归模型在提高反应温度下预测氨分解过程中氢气生成速率的潜力。利用文献数据库，我们对低温下收集的数据进行了顺序、随机和逆层次回归模型以及非层次模型的训练。对预测精度的比较表明，按温度升高组织的顺序分层模型提供了最高的精度。这一发现说明了该模型捕捉反应温度和催化性能之间非线性关系的能力。相比之下，随机和逆分层模型的性能都不如非分层模型，这突出了子集训练顺序对分层模型性能的重要性。研究子集配置、层次结构级别和算法类型对氨分解顺序层次模型预测精度的影响，有助于深入了解这些模型的优化设计。层次回归模型在催化性能预测中的成功应用证明了它们在捕捉多相催化数据库中固有的复杂性方面的优势。最终，层次模型在氨分解的各种反应温度下显示出强大的鲁棒性和可推广的预测潜力，扩展到原始训练领域之外。

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引用次数: 0