Applied Catalysis A: General最新文献_第3页

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 : 2026-02-25 Epub 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。

{"title":"Tailored acidity of silylated Pt/USY catalysts to regulate catalytic performances for phenol hydrogenation","authors":"Zhi Wang, Jun Chen, Gaolei Shi, Liuwei Shen, Xueqin Ma, Xingguang Zhang","doi":"10.1016/j.apcata.2026.120787","DOIUrl":"10.1016/j.apcata.2026.120787","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"712 ","pages":"Article 120787"},"PeriodicalIF":4.8,"publicationDate":"2026-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145974650","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

Reaction pathways of MoVTeNbO directed by Te defects for selective oxidation of toluene Te缺陷导向下的MoVTeNbO选择性氧化甲苯的反应途径

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-02-25 Epub Date: 2026-01-08 DOI: 10.1016/j.apcata.2026.120783

Changshun Deng , Chaoxiang Li , Haoyu Lu , Bingqing Ge , Weiping Ding

MoVTeNbO is a famous oxide of multi-component and effective for gaseous toluene oxidation to benzaldehyde, but exhibits catalytic properties highly sensitive to composition and surface properties. Here, we report the regulation of catalytic properties of MoVTeNbO by Te defects tuned in hydrothermal synthesis, even in the same bulk crystal structure of M1 phase, leading to significant difference in catalytic performance for selective oxidation of toluene using air as oxidant. The catalyst MoVTeNbO-1 in nano brick shape exhibits weaker redox capacity and acidity as well as lower contents of surface V^5 + and electrophilic oxygen species, giving rise to a conversion of toluene exceeding 8 % with a selectivity of 73 % to benzaldehyde at 350 °C. Nevertheless, the stronger oxidation capacity of MoVTeNbO-2 in nano firewood shape shows an outstanding activity for toluene oxidation at a conversion of ∼84 % and a selectivity more than 60 % to maleic anhydride at the same temperature. Further study indicates that much more Te defects in MoVTeNbO-2 play a key role for the regulation of its surface properties and direct the catalyst for toluene oxidation following totally different pathways of conversion. Results of characterizations including kinetics in-situ spectroscopy also indicate that the toluene oxidation over nano brick MoVTeNbO-1 follows an Eley-Rideal mechanism, but the toluene oxidation over nano firewood shaped MoVTeNbO-2 complies with a Langmuir-Hinshelwood mechanism.

MoVTeNbO是一种著名的多组分氧化物，对气态甲苯氧化制苯甲醛有效，但其催化性能对组分和表面性质高度敏感。在此，我们报道了在水热合成中，即使在相同的M1相体晶结构下，Te缺陷对MoVTeNbO的催化性能的调节，导致空气作为氧化剂选择性氧化甲苯的催化性能有显著差异。纳米砖状催化剂MoVTeNbO-1表现出较弱的氧化还原能力和酸性，表面V5 +和亲电氧含量较低，在350℃下甲苯转化为苯甲醛的选择性为73 %，转化率超过8 %。然而，纳米柴火形态的MoVTeNbO-2具有更强的氧化能力，在相同温度下对甲苯的转化率为~ 84 %，对马来酸酐的选择性超过60 %。进一步的研究表明，MoVTeNbO-2中更多的Te缺陷对其表面性能的调控起着关键作用，并指导了甲苯氧化催化剂经过完全不同的转化途径。动力学原位光谱等表征结果也表明，纳米砖状MoVTeNbO-1上的甲苯氧化符合Eley-Rideal机制，而纳米柴火状MoVTeNbO-2上的甲苯氧化符合Langmuir-Hinshelwood机制。

{"title":"Reaction pathways of MoVTeNbO directed by Te defects for selective oxidation of toluene","authors":"Changshun Deng , Chaoxiang Li , Haoyu Lu , Bingqing Ge , Weiping Ding","doi":"10.1016/j.apcata.2026.120783","DOIUrl":"10.1016/j.apcata.2026.120783","url":null,"abstract":"<div><div>MoVTeNbO is a famous oxide of multi-component and effective for gaseous toluene oxidation to benzaldehyde, but exhibits catalytic properties highly sensitive to composition and surface properties. Here, we report the regulation of catalytic properties of MoVTeNbO by Te defects tuned in hydrothermal synthesis, even in the same bulk crystal structure of M1 phase, leading to significant difference in catalytic performance for selective oxidation of toluene using air as oxidant. The catalyst MoVTeNbO-1 in nano brick shape exhibits weaker redox capacity and acidity as well as lower contents of surface V<sup>5 +</sup> and electrophilic oxygen species, giving rise to a conversion of toluene exceeding 8 % with a selectivity of 73 % to benzaldehyde at 350 °C. Nevertheless, the stronger oxidation capacity of MoVTeNbO-2 in nano firewood shape shows an outstanding activity for toluene oxidation at a conversion of ∼84 % and a selectivity more than 60 % to maleic anhydride at the same temperature. Further study indicates that much more Te defects in MoVTeNbO-2 play a key role for the regulation of its surface properties and direct the catalyst for toluene oxidation following totally different pathways of conversion. Results of characterizations including kinetics <em>in-situ</em> spectroscopy also indicate that the toluene oxidation over nano brick MoVTeNbO-1 follows an Eley-Rideal mechanism, but the toluene oxidation over nano firewood shaped MoVTeNbO-2 complies with a Langmuir-Hinshelwood mechanism.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"712 ","pages":"Article 120783"},"PeriodicalIF":4.8,"publicationDate":"2026-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145974700","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

Chalcone-based catalysts and functional nanomaterials for heavy-metal remediation: Mechanistic insights and environmental applications 重金属修复的查尔酮基催化剂和功能纳米材料：机理见解和环境应用

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-02-25 Epub Date: 2026-01-06 DOI: 10.1016/j.apcata.2026.120774

Elsayed G. Blall , Rafah Mohammed Thyab , Ahmed H. Abdel-Salam , Ahmed Morsy , Leonara de Oliveira Moura , Asmaa Mohamed , Ashraf Morsy

Heavy-metal contamination remains one of the most persistent global environmental challenges due to its toxicity, non-biodegradability, and accumulation in ecosystems. Conventional remediation techniques often struggle to achieve sustainable, selective, and efficient removal under realistic conditions. Chalcones, a subclass of flavonoids characterized by an α,β-unsaturated carbonyl framework, have recently attracted attention as multifunctional ligands capable of chelation, redox mediation, and surface interactions with transition metals. Recent studies have elucidated the mechanistic role of chalcone-based accelerators in cementation processes, particularly in enhancing catalytic activity and electron-transfer pathways for metal recovery. In parallel, chalcone-functionalized nanoparticles and hybrid nanocomposites have been reported to integrate adsorption, complexation, and redox mechanisms, enabling efficient removal of heavy metals such as Pb(II), Cd(II), and Cr(VI). Comparative analyses of adsorption kinetics, thermodynamic behavior, and regeneration performance reveal distinct advantages of chalcone-derived systems over conventional adsorbents, supported by molecular-level insights from density functional theory (DFT) and spectroscopic investigations. Current research trends indicate growing potential for incorporating chalcone-based nanomaterials into scalable water-treatment and resource-recovery applications, particularly through green synthesis approaches, stability enhancement, and cost-effective implementation.

重金属污染由于其毒性、不可生物降解性和在生态系统中的积累，仍然是最持久的全球环境挑战之一。在现实条件下，传统的修复技术往往难以实现可持续的、选择性的和有效的去除。查尔酮是一类以α，β-不饱和羰基骨架为特征的类黄酮，近年来作为具有螯合、氧化还原调解和与过渡金属表面相互作用的多功能配体而受到关注。最近的研究已经阐明了基于查尔酮的加速剂在胶结过程中的机制作用，特别是在提高金属回收的催化活性和电子转移途径方面。同时，据报道，查尔酮功能化纳米颗粒和杂化纳米复合材料具有吸附、络合和氧化还原机制，能够有效去除重金属，如Pb（II）、Cd（II）和Cr（VI）。吸附动力学、热力学行为和再生性能的对比分析表明，在密度泛函理论（DFT）和光谱研究的分子水平上，查尔酮衍生体系比传统吸附剂具有明显的优势。目前的研究趋势表明，将查尔酮基纳米材料纳入可扩展的水处理和资源回收应用的潜力越来越大，特别是通过绿色合成方法、稳定性增强和成本效益的实施。

{"title":"Chalcone-based catalysts and functional nanomaterials for heavy-metal remediation: Mechanistic insights and environmental applications","authors":"Elsayed G. Blall , Rafah Mohammed Thyab , Ahmed H. Abdel-Salam , Ahmed Morsy , Leonara de Oliveira Moura , Asmaa Mohamed , Ashraf Morsy","doi":"10.1016/j.apcata.2026.120774","DOIUrl":"10.1016/j.apcata.2026.120774","url":null,"abstract":"<div><div>Heavy-metal contamination remains one of the most persistent global environmental challenges due to its toxicity, non-biodegradability, and accumulation in ecosystems. Conventional remediation techniques often struggle to achieve sustainable, selective, and efficient removal under realistic conditions. Chalcones, a subclass of flavonoids characterized by an α,β-unsaturated carbonyl framework, have recently attracted attention as multifunctional ligands capable of chelation, redox mediation, and surface interactions with transition metals. Recent studies have elucidated the mechanistic role of chalcone-based accelerators in cementation processes, particularly in enhancing catalytic activity and electron-transfer pathways for metal recovery. In parallel, chalcone-functionalized nanoparticles and hybrid nanocomposites have been reported to integrate adsorption, complexation, and redox mechanisms, enabling efficient removal of heavy metals such as Pb(II), Cd(II), and Cr(VI). Comparative analyses of adsorption kinetics, thermodynamic behavior, and regeneration performance reveal distinct advantages of chalcone-derived systems over conventional adsorbents, supported by molecular-level insights from density functional theory (DFT) and spectroscopic investigations. Current research trends indicate growing potential for incorporating chalcone-based nanomaterials into scalable water-treatment and resource-recovery applications, particularly through green synthesis approaches, stability enhancement, and cost-effective implementation.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"712 ","pages":"Article 120774"},"PeriodicalIF":4.8,"publicationDate":"2026-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145903923","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 : 2026-02-25 Epub 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。

{"title":"Tailoring support defects in Ru/yttria–ceria catalysts for efficient and durable ammonia decomposition","authors":"Young Woo Kim , Eun-Jeong Kim , Sungjoon Kweon , Ho Jin Lee , Min Bum Park , Eun Duck Park , Chae-Ho Shin , Yongju Yun","doi":"10.1016/j.apcata.2026.120791","DOIUrl":"10.1016/j.apcata.2026.120791","url":null,"abstract":"<div><div>The catalytic decomposition of ammonia (NH<sub>3</sub>) 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 CeO<sub>2</sub> 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/<em>a</em>Y-CeO<sub>x</sub>) by systematically varying the Y content of the support. Incorporating Y<sup>3+</sup> into the CeO<sub>2</sub> 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<sub>x</sub> catalyst achieves 80 % NH<sub>3</sub> conversion at 450 °C with a hydrogen formation rate of 10.8 mmol∙g<sub>cat</sub><sup>−1</sup>∙min<sup>−1</sup> 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 N<sub>2</sub> desorption, and mitigates H<sub>2</sub> 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.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"712 ","pages":"Article 120791"},"PeriodicalIF":4.8,"publicationDate":"2026-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145974116","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

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 : 2026-02-25 Epub 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":"2026-02-25","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

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 : 2026-02-25 Epub 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。

{"title":"Exploring the catalytic chan-lam coupling reaction of N-Arylation of amines using heterogeneous thiophene schiff base-Ni-bipy complex on mesoporous MCM-41","authors":"Narmatha Venkatesan, Rajashri Varadarasu, Jayapratha Gunasekaran, Shanmuga Bharathi Kuppannan","doi":"10.1016/j.apcata.2026.120793","DOIUrl":"10.1016/j.apcata.2026.120793","url":null,"abstract":"<div><div>The present work is planned to examine the <em>N</em>-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), N<sub>2</sub> adsorption–desorption isotherm (BET), and X-ray photoelectron spectroscopy (XPS) techniques. The catalytic efficiency of the compound was assessed in <em>N</em>-arylation of amines using phenylboronic acid with various substituted amines (viz. electron donating/ withdrawing, fused ring, heterocyclic and aliphatic substituents), K<sub>2</sub>CO<sub>3</sub> 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 <em>N</em>-arylation of amines and the comparison of catalytic efficiency of our catalyst against some notable reported catalysts were also discussed.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"712 ","pages":"Article 120793"},"PeriodicalIF":4.8,"publicationDate":"2026-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035280","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

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 : 2026-02-25 Epub 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。

{"title":"Efficient hydrogen generation via steam reforming of ultra-stable emulsified hydrocarbon fuel catalyzed by NixPt1-x/Al2O3","authors":"Hongshang Wang , Jingkai Ma , Ruihan Lv , Ji Mi , Wenjun Fang","doi":"10.1016/j.apcata.2026.120794","DOIUrl":"10.1016/j.apcata.2026.120794","url":null,"abstract":"<div><div>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<sub>0.93</sub>Pt<sub>0.07</sub>/Al<sub>2</sub>O<sub>3</sub> 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<sup>−1</sup> 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<sup>−1</sup> of H<sub>2</sub>. 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<sub><em>x</em></sub>* intermediates to undergo further dehydrogenation into carbonaceous deposits, facilitating their effective removal.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"712 ","pages":"Article 120794"},"PeriodicalIF":4.8,"publicationDate":"2026-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035602","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

Ligand-engineered cobalt precursors toward enhanced catalytic activity of Co@S-1 zeolite in toluene oxidation 配体工程钴前驱体增强Co@S-1沸石对甲苯氧化的催化活性

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-02-25 Epub Date: 2026-01-08 DOI: 10.1016/j.apcata.2026.120784

Shengnan Xu, Yu Yu, Fuxin Wang, Jiande Hu, Zixiang Li, Guojun Lv

Cobalt-doped zeolite catalysts have been identified as a potentially viable non-precious metal alternative for toluene oxidation, exhibiting characteristics reminiscent of noble metals, such as the ability to activate C-H bonds, abundance, and minimal adverse environmental impact. However, the catalytic activity is greatly reliant on the diversity of cobalt species embedded within the zeolite framework. To address this, a ligand-engineering strategy was utilized to precisely control the coordination environment of the cobalt precursor, thereby regulating the resulting cobalt species and accordingly the catalytic activity of cobalt-doped zeolite catalysts. Four distinct Co@S-1 zeolites were synthesized with disparate ligands including ethylenediamine, water, ammonia water and acetylacetone, and meanwhile applied as heterogeneous catalysts for the selective oxidation of toluene with molecular oxygen as oxidant. Among them, the Co@S-1(EDA) zeolite catalyst synthesized with ethylenediamine demonstrated superior catalytic reaction performance, achieving a toluene conversion of 63.8 % with a benzaldehyde selectivity of 68.5 % within 6 h of reaction. This eminent catalytic oxidation ability for Co@S-1(EDA) zeolite catalyst is mainly ascribed to its largest Co²⁺/Co³⁺ ratio, its most oxygen vacancy amount and its largest external surface area. Furthermore, the Co@S-1(EDA) zeolite catalyst exhibited excellent re-usability, maintaining its activity over five consecutive catalytic cycles. This study emphasizes ligand engineering as an effective approach to create highly efficient and stable cobalt-based zeolite catalysts for selective hydrocarbon oxidation reactions.

钴掺杂沸石催化剂已被确定为甲苯氧化的潜在可行的非贵金属替代品，表现出贵金属的特征，如激活C-H键的能力，丰度和最小的不利环境影响。然而，催化活性很大程度上依赖于嵌入在沸石框架内的钴物种的多样性。为了解决这个问题，采用配体工程策略来精确控制钴前驱体的配位环境，从而调节所得到的钴种类，从而调节钴掺杂沸石催化剂的催化活性。以乙二胺、水、氨水和乙酰丙酮为配体合成了四种不同的Co@S-1沸石，并将其作为异相催化剂应用于以分子氧为氧化剂选择性氧化甲苯。其中，以乙二胺为原料合成的Co@S-1（EDA）分子筛催化剂表现出优异的催化反应性能，在反应6 h内，甲苯转化率为63.8 %，苯甲醛选择性为68.5 %。Co@S-1（EDA）沸石催化剂之所以具有优异的催化氧化能力，主要是由于其最大的Co2+/Co3+比、最大的氧空位量和最大的外表面积。此外，Co@S-1（EDA）沸石催化剂表现出优异的可重复使用性，在连续五个催化循环中保持其活性。本研究强调配体工程是制备高效稳定的钴基沸石催化剂用于选择性烃类氧化反应的有效途径。

{"title":"Ligand-engineered cobalt precursors toward enhanced catalytic activity of Co@S-1 zeolite in toluene oxidation","authors":"Shengnan Xu, Yu Yu, Fuxin Wang, Jiande Hu, Zixiang Li, Guojun Lv","doi":"10.1016/j.apcata.2026.120784","DOIUrl":"10.1016/j.apcata.2026.120784","url":null,"abstract":"<div><div>Cobalt-doped zeolite catalysts have been identified as a potentially viable non-precious metal alternative for toluene oxidation, exhibiting characteristics reminiscent of noble metals, such as the ability to activate C-H bonds, abundance, and minimal adverse environmental impact. However, the catalytic activity is greatly reliant on the diversity of cobalt species embedded within the zeolite framework. To address this, a ligand-engineering strategy was utilized to precisely control the coordination environment of the cobalt precursor, thereby regulating the resulting cobalt species and accordingly the catalytic activity of cobalt-doped zeolite catalysts. Four distinct Co@S-1 zeolites were synthesized with disparate ligands including ethylenediamine, water, ammonia water and acetylacetone, and meanwhile applied as heterogeneous catalysts for the selective oxidation of toluene with molecular oxygen as oxidant. Among them, the Co@S-1(EDA) zeolite catalyst synthesized with ethylenediamine demonstrated superior catalytic reaction performance, achieving a toluene conversion of 63.8 % with a benzaldehyde selectivity of 68.5 % within 6 h of reaction. This eminent catalytic oxidation ability for Co@S-1(EDA) zeolite catalyst is mainly ascribed to its largest Co<sup>2+</sup>/Co<sup>3+</sup> ratio, its most oxygen vacancy amount and its largest external surface area. Furthermore, the Co@S-1(EDA) zeolite catalyst exhibited excellent re-usability, maintaining its activity over five consecutive catalytic cycles. This study emphasizes ligand engineering as an effective approach to create highly efficient and stable cobalt-based zeolite catalysts for selective hydrocarbon oxidation reactions.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"712 ","pages":"Article 120784"},"PeriodicalIF":4.8,"publicationDate":"2026-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145974697","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

Synergy of confinement effect and oxygen vacancy in carboxymethyl-β-cyclodextrin-intercalated CoAl-LDH for boosting selective aerobic oxidation of alcohols in water 羧甲基-β-环糊精插层煤- ldh约束效应和氧空位协同促进醇在水中的选择性好氧氧化

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-02-25 Epub Date: 2026-01-05 DOI: 10.1016/j.apcata.2026.120771

Fang Fang, Dongping Sun, Xinhua Peng

Selective catalytic aerobic oxidation of alcohols into aldehydes and ketones using water as solvent and layered double hydroxides as alkaline catalyst exemplifies both atom economy and environmental benignity. In this work, we initially synthesized oxygen vacancy-rich monolayer m-CoAl-LDH nanosheets through a facile direct synthesis method. Then, by reassembling the CMCD anions with m-CoAl-LDH layers to form an oxygen vacancy-rich heterogeneous CMCD-CoAl-LDH intercalation hybrid. We investigated the application of CMCD-CoAl-LDH in the aerobic oxidation of alcohol in water, and examined the structure-activity relationship. The oxygen vacancy defect sites on the LDH layers activate both oxygen and alcohol molecules. Concurrently, CMCD with LDH layers collaboratively form a confined environment, exerting the confinement effect to achieve highly efficient and selective aerobic oxidation. The adsorption and surface reaction of benzyl alcohol on the catalyst in an O₂ atmosphere were investigated by in situ DRIFT spectroscopy. DFT calculation of adsorption energy reveals that oxygen vacancies serve as the primary sites for the adsorption of benzyl alcohol and oxygen molecules. This catalyst system demonstrates excellent compatibility with green aqueous media and significantly promotes the aerobic oxidation of alcohol. It provides a feasible paradigm of integrating supramolecular chemistry with materials chemistry to address challenges in catalysis.

以水为溶剂，层状双氢氧化物为碱性催化剂，选择性地催化好氧氧化醇生成醛和酮，这是原子经济性和环境友好性的例证。在这项工作中，我们首次通过简单的直接合成方法合成了富氧空位的单层m-煤- ldh纳米片。然后，通过将CMCD阴离子与m-CoAl-LDH层重组，形成富氧空位的非均相CMCD- coal - ldh插层杂化物。研究了CMCD-CoAl-LDH在水中乙醇好氧氧化中的应用，并考察了其构效关系。LDH层上的氧空位缺陷位点同时激活氧和醇分子。同时，CMCD与LDH层协同形成密闭环境，发挥约束作用，实现高效选择性好氧氧化。采用原位漂移光谱法研究了甲醇在O2气氛下在催化剂上的吸附和表面反应。吸附能的DFT计算表明，氧空位是苯甲醇和氧分子吸附的主要位置。该催化剂体系与绿色水介质具有良好的相容性，并能显著促进醇的好氧氧化。它提供了一个将超分子化学与材料化学相结合的可行范例，以解决催化方面的挑战。

{"title":"Synergy of confinement effect and oxygen vacancy in carboxymethyl-β-cyclodextrin-intercalated CoAl-LDH for boosting selective aerobic oxidation of alcohols in water","authors":"Fang Fang, Dongping Sun, Xinhua Peng","doi":"10.1016/j.apcata.2026.120771","DOIUrl":"10.1016/j.apcata.2026.120771","url":null,"abstract":"<div><div>Selective catalytic aerobic oxidation of alcohols into aldehydes and ketones using water as solvent and layered double hydroxides as alkaline catalyst exemplifies both atom economy and environmental benignity. In this work, we initially synthesized oxygen vacancy-rich monolayer m-CoAl-LDH nanosheets through a facile direct synthesis method. Then, by reassembling the CMCD anions with m-CoAl-LDH layers to form an oxygen vacancy-rich heterogeneous CMCD-CoAl-LDH intercalation hybrid. We investigated the application of CMCD-CoAl-LDH in the aerobic oxidation of alcohol in water, and examined the structure-activity relationship. The oxygen vacancy defect sites on the LDH layers activate both oxygen and alcohol molecules. Concurrently, CMCD with LDH layers collaboratively form a confined environment, exerting the confinement effect to achieve highly efficient and selective aerobic oxidation. The adsorption and surface reaction of benzyl alcohol on the catalyst in an O<sub>2</sub> atmosphere were investigated by in situ DRIFT spectroscopy. DFT calculation of adsorption energy reveals that oxygen vacancies serve as the primary sites for the adsorption of benzyl alcohol and oxygen molecules. This catalyst system demonstrates excellent compatibility with green aqueous media and significantly promotes the aerobic oxidation of alcohol. It provides a feasible paradigm of integrating supramolecular chemistry with materials chemistry to address challenges in catalysis.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"712 ","pages":"Article 120771"},"PeriodicalIF":4.8,"publicationDate":"2026-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145941062","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

Novel advanced channel reactor for spatio-temporal activity and catalyst state correlations applied for the reduction of NO by CO over Pt/Al2O3 新型先进的通道反应器用于Pt/Al2O3上CO还原NO的时空活性和催化剂状态相关性

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-02-25 Epub Date: 2025-12-20 DOI: 10.1016/j.apcata.2025.120748

Thomas Häber , Sui Wan , Samuel Struzek , Camilo Cárdenas , Anna Zimina , Florian Maurer , Patrick Lott , Rainer Suntz , Jan-Dierk Grunwaldt , Olaf Deutschmann

The correlation of space- and time-resolved measurements of catalytic activity with catalyst state is an invaluable tool to advance the understanding and development of complex catalytic systems under conditions relevant to technical applications. Such an approach is employed here to investigate the catalytic deactivation in the reduction of NO by CO over Pt/Al₂O₃ on freshly reduced catalysts in a channel reactor and at concentrations typical for emission control. Planar laser-induced fluorescence (PLIF) is used to visualize the 2D concentration profiles and to derive space- and time-resolved NO conversion rates for different CO/NO ratios, temperatures and mass flow rates. The changes in catalytic activity are correlated with temporal and spatial changes in oxidation state determined by operando X-ray absorption spectroscopy (XAS) under the same conditions. The time scales of the changes in catalytic activity depend not only on the stoichiometry and temperature, but also on the position along the catalyst channel and differ significantly from the temporal changes of the oxidation state. The different time scales are discussed in the context of the known CO poisoning as well as the formation and storage of isocyanate on the support. Isocyanate formation temporarily counteracting CO poisoning could explain the differences in the observed time scales under different reaction conditions and at different locations on the catalyst.

在与技术应用相关的条件下，空间和时间分辨的催化活性测量与催化剂状态的相关性是促进对复杂催化系统的理解和发展的宝贵工具。本文采用这种方法，在通道反应器中，在典型的排放控制浓度下，研究了CO在Pt/Al2O3上新还原的催化剂上还原NO的催化失活。平面激光诱导荧光（PLIF）用于可视化二维浓度分布，并推导出不同CO/NO比、温度和质量流量下的空间和时间分辨NO转化率。在相同条件下，用x射线吸收光谱（XAS）测定氧化态的时空变化与催化活性的变化相关。催化活性变化的时间尺度不仅取决于化学计量和温度，还取决于催化剂通道上的位置，与氧化态的时间变化有很大的不同。在已知CO中毒以及异氰酸酯在载体上的形成和储存的背景下，讨论了不同的时间尺度。异氰酸酯的形成可以暂时抵消CO中毒，这可以解释不同反应条件下和催化剂上不同位置观察到的时间尺度的差异。

{"title":"Novel advanced channel reactor for spatio-temporal activity and catalyst state correlations applied for the reduction of NO by CO over Pt/Al2O3","authors":"Thomas Häber , Sui Wan , Samuel Struzek , Camilo Cárdenas , Anna Zimina , Florian Maurer , Patrick Lott , Rainer Suntz , Jan-Dierk Grunwaldt , Olaf Deutschmann","doi":"10.1016/j.apcata.2025.120748","DOIUrl":"10.1016/j.apcata.2025.120748","url":null,"abstract":"<div><div>The correlation of space- and time-resolved measurements of catalytic activity with catalyst state is an invaluable tool to advance the understanding and development of complex catalytic systems under conditions relevant to technical applications. Such an approach is employed here to investigate the catalytic deactivation in the reduction of NO by CO over Pt/Al<sub>2</sub>O<sub>3</sub> on freshly reduced catalysts in a channel reactor and at concentrations typical for emission control. Planar laser-induced fluorescence (PLIF) is used to visualize the 2D concentration profiles and to derive space- and time-resolved NO conversion rates for different CO/NO ratios, temperatures and mass flow rates. The changes in catalytic activity are correlated with temporal and spatial changes in oxidation state determined by <em>operando</em> X-ray absorption spectroscopy (XAS) under the same conditions. The time scales of the changes in catalytic activity depend not only on the stoichiometry and temperature, but also on the position along the catalyst channel and differ significantly from the temporal changes of the oxidation state. The different time scales are discussed in the context of the known CO poisoning as well as the formation and storage of isocyanate on the support. Isocyanate formation temporarily counteracting CO poisoning could explain the differences in the observed time scales under different reaction conditions and at different locations on the catalyst.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"712 ","pages":"Article 120748"},"PeriodicalIF":4.8,"publicationDate":"2026-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145940922","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