Applied Catalysis A: General最新文献_第2页

Tunable oxidation pathways via ligand-assisted stabilization of Mn(III)/Mn(V) in a permanganate/sulfite process for robust water treatment 在高锰酸盐/亚硫酸盐工艺中，通过配体辅助稳定Mn(III)/Mn(V)的可调氧化途径用于稳健水处理

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-03-05 Epub Date: 2026-01-27 DOI: 10.1016/j.apcata.2026.120811

Junren Zhu , Zhenzhen Jiang , Chaohan Jiang , Hongxiang Zeng , Wei Ding , Xintao Tan , Xinyi Li , Faxiang Zhang

Radical-dependent advanced oxidation processes (AOPs) have emerged as promising technologies for water decontamination, yet remain constrained by critical limitations, including susceptibility to matrix quenching and the formation of toxic byproducts, which hinder their broad application. To address these challenges, this study engineers a ligand-stabilized permanganate/sulfite (Mn(VII)/S(IV)) system using nitrilotriacetic acid (NTA) for efficient degradation of recalcitrant organic pollutants across a wide pH range. The NTA coordination critically stabilizes reactive Mn intermediates (Mn(III) and Mn(V)), generated via two-electron reduction of Mn(VII) by S(IV), effectively mitigating their deactivation through hydrolysis or disproportionation at near-neutral pH. This stabilization enables sustained catalytic activity from pH 4–7.5, overcoming the strict acidic pH requirement of conventional Mn(VII)/S(IV) systems. Mechanistic investigations reveal dual oxidation pathways: Mn(III)–NTA species mediate radical-based oxidation through SO₄^•− generation, while Mn(V)−NTA species dominate non-radical two-electron oxidation process. Crucially, the Mn(VII)/S(IV) molar ratio serves as a tunable lever governing oxidation pathway selection: higher ratios favor non-radical Mn(V)−NTA oxidation, whereas lower ratios promote SO₄^•−-based pathways that are subject to self-quenching by excess S(IV). Dissolved oxygen further sustains the catalytic cycles by preventing premature Mn(V) reduction and facilitating oxysulfur radical chain propagation. Moreover, the NTA coordination confers exceptional resilience against common water matrix interferents (e.g., anions and natural organic maters), while maintaining high degradation efficacy in diverse natural waters. This work demonstrates that ligand-stabilized high-valent Mn(V) catalysis enables tunable and robust oxidation pathways, providing new mechanistic insights for precision oxidation technologies.

自由基依赖的高级氧化工艺（AOPs）已经成为一种很有前途的水净化技术，但仍然受到一些关键限制，包括对基体淬火的敏感性和有毒副产物的形成，这些限制阻碍了它们的广泛应用。为了解决这些挑战，本研究设计了一种配体稳定的高锰酸盐/亚硫酸盐(Mn（VII)/S(IV)）系统，使用硝基三乙酸（NTA）在很宽的pH范围内有效降解顽固性有机污染物。NTA配位对S（IV）还原Mn（VII）生成的活性Mn中间体（Mn（III）和Mn(V)）具有重要的稳定作用，有效地缓解了它们在接近中性pH下因水解或歧化而失活的情况。这种稳定性使其在pH 4-7.5范围内保持催化活性，克服了传统Mn(VII)/S（IV）体系对酸性pH的严格要求。机理研究揭示了双重氧化途径：Mn(III) -NTA通过SO4•−生成介导自由基氧化，而Mn(V) -NTA主导非自由基双电子氧化过程。至关重要的是，Mn(VII)/S（IV）的摩尔比可以作为控制氧化途径选择的可调杠杆：较高的摩尔比有利于非自由基Mn(V) - NTA氧化，而较低的摩尔比促进SO4•−为基础的氧化途径，这些途径受到过量S（IV）的自猝灭。溶解氧通过防止Mn(V)过早还原和促进氧硫自由基链的传播进一步维持催化循环。此外，NTA配位对常见的水基质干扰（如阴离子和天然有机物质）具有特殊的弹性，同时在不同的自然水域保持高降解效率。这项工作表明，配体稳定的高价Mn(V)催化能够实现可调和稳健的氧化途径，为精密氧化技术提供了新的机制见解。

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引用次数: 0

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

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-03-05 Epub Date: 2026-01-21 DOI: 10.1016/j.apcata.2026.120797

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

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

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

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引用次数: 0

Synthesis of methyl glycolate via dimethyl oxalate hydrogenation over Zr‑modified Ag/SiO2 catalysts Zr改性Ag/SiO2催化剂上草酸二甲酯加氢合成乙醇酸甲酯

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-03-05 Epub Date: 2026-01-08 DOI: 10.1016/j.apcata.2025.120765

Lei Shi , Jinyu Sun , Xiguang Wang , Xinyi Cao , Jiankai Cheng , Yong Gao , Luyang Qiao , Zhangfeng Zhou , Yuangen Yao

Semi-hydrogenation of dimethyl oxalate (DMO) is an attractive route for methyl glycolate (MG) synthesis. However, constructing efficient catalyst remains a great challenge. Herein, a series of Ag-xZr/SiO₂ catalysts were prepared via the ammonia evaporation method and the effects of Zr doping over Ag/SiO₂ catalysts are investigated. Characterization results indicated that Zr doping promotes the formation of Ag₁₀Si₄O₁₃ species, which played a key role in regulating the Ag⁰ / Ag⁺ ratio and promoting the Ag dispersion. Moreover, Zr doped SiO₂ generated strengthened Lewis acids (LA) for DMO activation and more Brønsted acids (BA) for H transfer. In comparison, over-doping may promote the growth of Ag particles due to changed coordination environment of Ag-O. With an optimal Zr content, the Ag-3Zr/SiO₂ catalyst achieves 99 % DMO conversion with over 90 % MG yield under a WHSV of 1.0 mL·g⁻¹ ·h⁻¹ . This work offered valuable insights about the balances of Ag⁰ and Ag⁺, as well as LA and BA for designing efficient catalysts for DMO semi-hydrogenation.

草酸二甲酯（DMO）半加氢是合成乙醇酸甲酯（MG）的有效途径。然而，构建高效的催化剂仍然是一个巨大的挑战。本文采用氨蒸发法制备了一系列Ag- xzr /SiO2催化剂，并考察了Zr掺杂对Ag/SiO2催化剂性能的影响。表征结果表明，Zr掺杂促进了Ag10Si4O13物质的形成，这对调节Ag0 / Ag⁺的比例、促进Ag的分散起到了关键作用。此外，Zr掺杂SiO2产生了增强的用于DMO活化的Lewis酸（LA）和更多用于H转移的Brønsted酸（BA）。相比之下，过量掺杂会改变Ag- o的配位环境，从而促进Ag粒子的生长。在Zr含量最优的情况下，Ag-3Zr/SiO2催化剂在1.0 mL·g⁻¹ ·h⁻ 的WHSV下，DMO转化率达到99% %，MG收率超过90% %。这项工作为设计有效的DMO半加氢催化剂提供了有关Ag0和Ag+平衡以及LA和BA的有价值的见解。

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引用次数: 0

Dry reforming of methane over Ni-Mg-O and Ni-Ce-Mg-O oxide catalysts: Effect of the calcination temperature on the catalytic performance and thermal stability Ni-Mg-O和Ni-Ce-Mg-O氧化物催化剂上甲烷干重整：煅烧温度对催化性能和热稳定性的影响

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-03-05 Epub Date: 2026-01-22 DOI: 10.1016/j.apcata.2026.120801

Grigory B. Veselov, Ekaterina V. Ilyina, Vladimir O. Stoyanovskii, Aleksey A. Vedyagin

Sol-gel-prepared Ni-Mg-O oxide systems are considered promising catalysts for dry reforming of methane. The addition of CeO₂ to the catalyst composition enhances its performance under reaction conditions. Another factor affecting the activity and thermal stability of such catalysts is the strength of the NiO-MgO interaction. In this research, the effects of calcination temperature on the textural characteristics, strength of NiO-MgO interaction, and catalytic performance of Ni-Mg-O and Ni-Ce-Mg-O in the dry reforming of methane are studied. As found, the sintering resistance of MgO is noticeably enhanced in the presence of CeO₂. Moreover, CeO₂ hinders the formation of Ni_xMg_1-xO solid solutions, thus improving the reducibility of Ni. The strength of the NiO-MgO interaction increased with the temperature for both the Ni-Mg-O and Ni-Ce-Mg-O samples, while the NiO-CeO₂ interaction was optimal after calcination at 600 °C. The increased stability of the CeO₂-containing catalyst under dry reforming conditions is due to the suppressed formation of carbon deposits. Among the Ce-containing catalysts, the samples calcined at 500 and 600 °С exhibited an optimal catalytic performance. Thus, the former demonstrated a higher conversion of the reagents, while the latter showed a higher stability. At a higher calcination temperature (700 °С), the weaker NiO-CeO₂ and NiO-MgO interactions worsened both the stability and catalytic activity. The Ni-Ce-Mg-O sample calcined at 600 °C was tested at 30 L/(g·h) and 750 °C for 140 h and demonstrated the values of CH₄ and CO₂ conversions of 89.6 and 90.2 %, respectively. As revealed by high-resolution transmission electron microscopy, regardless of calcination temperature, reduction of CeO₂ in hydrogen at 750 °C has led to the formation of highly dispersed clusters along with layers at the intra-crystallite boundaries. The interaction of these CeO₂ species with Ni is supposed to be responsible for the enhanced catalytic performance.

溶胶-凝胶法制备的Ni-Mg-O氧化物体系被认为是很有前途的甲烷干重整催化剂。在反应条件下，CeO2的加入提高了催化剂的性能。影响催化剂活性和热稳定性的另一个因素是NiO-MgO相互作用的强度。本研究研究了煅烧温度对Ni-Mg-O和Ni-Ce-Mg-O在甲烷干重整中的结构特征、相互作用强度以及催化性能的影响。结果表明，在CeO2的存在下，MgO的抗烧结性能明显增强。此外，CeO2阻碍了NixMg1-xO固溶体的形成，从而提高了Ni的还原性。Ni-Mg-O和Ni-Ce-Mg-O样品的NiO-MgO相互作用强度随温度的升高而增加，而NiO-CeO2相互作用在600℃煅烧后达到最佳。在干重整条件下，含ceo2催化剂稳定性的提高是由于抑制了碳沉积的形成。在含ce催化剂中，500°和600°С煅烧的样品表现出最佳的催化性能。因此，前者表现出较高的试剂转化率，而后者表现出较高的稳定性。在较高的煅烧温度（700°С）下，较弱的NiO-CeO2和NiO-MgO相互作用使催化剂的稳定性和催化活性恶化。将Ni-Ce-Mg-O样品在600℃下焙烧30 L/(g·h)， 750℃下焙烧140 h， CH4和CO2转化率分别为89.6和90.2 %。高分辨率透射电镜显示，无论煅烧温度如何，750°C时CeO2在氢中的还原导致在晶内边界形成高度分散的团簇和层。这些CeO2与Ni的相互作用被认为是催化性能增强的原因。

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引用次数: 0

Aldol condensation of formaldehyde with propionaldehyde catalyzed by an efficient sulfonic acid resin catalyst 高效磺酸树脂催化剂催化甲醛与丙醛的醛缩反应

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-03-05 Epub Date: 2026-02-03 DOI: 10.1016/j.apcata.2026.120822

Zhiwen Luo, Gang Li, Hongxian Luo, Yuhan Qiao

In this work, a simple and green method for the preparation of sulfonic acid resin catalysts with tunable acid density was developed. The characterization techniques, including XRD, FT-IR, solid-state ¹³C CP/MAS NMR, TG-MS, SEM, and N₂ physisorption, was employed to present the catalyst's framework structure, microscopic morphology, and pore size distribution. The catalyst poly(DVB-PSSA₃)_s consists of stacked nanoparticles approximately 100 nm in size, with C, O, S elements uniformly distributed throughout its structure, a specific surface area of 29 m² g⁻¹, and a pore volume of 0.28 cm³ g⁻¹. Furthermore, the acid strength and acid density were quantitatively determined using the Hammett indicator method and acid-base titration, revealing H₀ = 0.08 and [H⁺] = 3.25 mmol g⁻¹ for the poly(DVB-PSSA₃)_s catalyst. In the aldol condensation reaction of formaldehyde and propionaldehyde, the catalyst exhibited no significant loss in activity during a 120-hour continuous test. A methacrolein selectivity of 98 % and yield of 92.3 % could be achieved under optimal conditions. Furthermore, the catalyst also demonstrated excellent catalytic activity in the reaction of formaldehyde with isobutyraldehyde, yielding a hydroxypivalaldehyde (HPA) selectivity of 95 %. These findings suggest the potential applicability of this catalyst in series of aldol condensation reactions.

本文研究了一种简单、绿色的酸密度可调磺酸树脂催化剂的制备方法。采用XRD、FT-IR、固态13C CP/MAS NMR、TG-MS、SEM、N2物理吸附等表征技术表征催化剂的骨架结构、微观形貌和孔径分布。催化剂poly(DVB-PSSA3)s由大小约为100 nm的纳米颗粒堆叠而成，C、O、s元素均匀分布在整个结构中，比表面积为29 m2 g−1，孔体积为0.28 cm3 g−1。采用Hammett指示剂法和酸碱滴定法定量测定了poly(DVB-PSSA3)s催化剂的酸强度和酸密度，得到了H0 = 0.08和[H+] = 3.25 mmol g−1。在甲醛和丙醛的醛缩反应中，催化剂在120小时的连续测试中没有表现出明显的活性损失。在此条件下，甲基丙烯醛的选择性为98 %，收率为92.3 %。此外，该催化剂在甲醛与异丁醛的反应中也表现出优异的催化活性，羟基戊醛（HPA）的选择性为95% %。这些发现表明该催化剂在一系列醛缩反应中具有潜在的适用性。

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引用次数: 0

Efficient debromination of tetrabromobisphenol A in protic solvents by supported nickel catalysts: Effect of metal-support interactions 负载镍催化剂在质子溶剂中高效脱溴四溴双酚A：金属-负载相互作用的影响

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-03-05 Epub Date: 2026-01-30 DOI: 10.1016/j.apcata.2026.120818

Paavo Auvinen , Eerika Olkkonen , Konstantin Tamarov , Ida M. Uotila , Ville H. Nissinen , Jani Pelto , Vesa-Pekka Lehto , Mika Suvanto , Janne Jänis , Jarkko J. Saarinen

Toxic and environmentally hazardous brominated flame retardants (BFR) hinder the recycling of plastic waste, which has led to the development of various extraction processes to remove them. These processes can be further advanced by debrominating BFRs into less harmful compounds with potential commercial value, thus supporting the principles of a circular economy. Herein, Ni/Al₂O₃ was employed for the catalytic debromination of tetrabromobisphenol A flame retardant in mixtures of H₂O, isopropanol and NaOH at modest reaction temperatures. Activity experiments conducted in an autoclave indicated that studied catalyst exhibits impressive debromination activity and complete selectivity towards C−Br bond scission. The catalyst reduction temperature was found to correlate with debromination activity, with higher temperatures yielding improved performance. Debromination proceeded under H₂ and also under N₂ in protic solvents via transfer hydrogenation. Catalyst characterization, coupled with high-resolution mass-spectrometry product analytics and deuterium labelling, suggested that the enhanced catalytic activity can be attributed to the activation of the metal-support interface and subsequent interactions with adsorbed solvent molecules and associated dissociation products on the alumina support. Used experimental conditions also provided high tolerance against bromine poisoning of the catalyst, in contrast to reference debromination experiments conducted in toluene. The study demonstrates the capability of Ni/Al₂O₃ as an efficient and affordable debromination catalyst in solvents of low environmental impact. Furthermore, the results provide additional insights into structure-activity relationships of supported nickel catalysts in protic solvents, which can be leveraged for the development of more efficient and sustainable dehalogenation and heteroatom removal processes for environmental applications.

有毒和对环境有害的溴化阻燃剂（BFR）阻碍了塑料废物的回收利用，这导致了各种提取工艺的发展，以去除它们。这些过程可以通过将溴化燃料分解成具有潜在商业价值的危害较小的化合物来进一步推进，从而支持循环经济的原则。本文采用Ni/Al2O3在水、异丙醇和NaOH的混合物中催化脱溴四溴双酚A阻燃剂，反应温度适中。在高压灭菌器中进行的活性实验表明，所研究的催化剂具有令人印象深刻的脱溴活性和对C - Br键断裂的完全选择性。发现催化剂还原温度与脱溴活性相关，温度越高，性能越好。在质子溶剂中，通过转移加氢，在H2和N2条件下进行脱溴。催化剂表征，结合高分辨率质谱产物分析和氘标记，表明催化活性的增强可归因于金属载体界面的活化以及随后与氧化铝载体上吸附的溶剂分子和相关解离产物的相互作用。与在甲苯中进行的参考脱溴实验相比，所使用的实验条件还提供了对催化剂溴中毒的高耐受性。该研究证明了Ni/Al2O3在低环境影响溶剂中作为一种高效、经济的脱溴催化剂的能力。此外，该结果还为质子溶剂中负载型镍催化剂的构效关系提供了额外的见解，可用于开发更有效和可持续的环境应用脱卤和杂原子去除工艺。

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引用次数: 0

Fe-Cu interaction in SSZ-13 enhanced reactivity and H2O tolerance during catalytic combustion of dichloromethane SSZ-13中Fe-Cu相互作用增强了二氯甲烷催化燃烧的反应活性和耐水能力

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-03-05 Epub Date: 2026-01-26 DOI: 10.1016/j.apcata.2026.120803

Peng-Ge Li , Yi-Fan Yao , Hui Wu, Long-Ren OuYang, Ai-Ping Jia, Yu Wang, Ji-Qing Lu

Bimetallic Fe-Cu modified SSZ-13 catalyst (FeCu-SSZ-13) was prepared by a sequential ion-exchange method and tested for catalytic oxidation of dichloromethane. It was found that the FeCu-SSZ-13 catalyst was more active than the Cu- and Fe-SSZ-13 catalysts, giving a very high reaction rate of 5.04 mmol_CH2Cl2 g_cat⁻¹ h⁻¹ at 250 °C. The catalyst was highly resistant to water vapor during the reaction, thus showing potential in practical application. The improved performance was attributed to the strong Fe-Cu interaction, not only enhancing the surface acidity and redox capability of the catalyst for higher activity, but stabilizing isolated Cu cations for better catalyst stability particularly under wet condition. Moreover, the in situ spectroscopic investigation on the reaction route revealed that C-Cl cleavage on the surface acid site while the oxidation of reactive intermediates is related to metal cations, which thus showed a clear synergy and accounted for higher mineralization rate.

采用顺序离子交换法制备了双金属Fe-Cu修饰的SSZ-13催化剂（FeCu-SSZ-13），并对其催化氧化二氯甲烷进行了实验研究。结果表明，FeCu-SSZ-13催化剂比Cu-和Fe-SSZ-13催化剂活性更高，在250 °C时反应速率为5.04 mmolCH2Cl2 gcat−1 h−1。该催化剂在反应过程中具有较强的抗水蒸气性，具有实际应用潜力。Fe-Cu之间的强相互作用不仅提高了催化剂的表面酸度和氧化还原能力，提高了催化剂的活性，而且稳定了分离的Cu阳离子，提高了催化剂的稳定性，特别是在湿条件下。此外，对反应路线的原位光谱研究表明，C-Cl在表面酸位解理，而反应中间体的氧化与金属阳离子有关，因此表现出明显的协同作用，并导致较高的矿化率。

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引用次数: 0

Vanadium as a superior promoter in LaFeO3 perovskite for “low-temperature” H2S catalytic oxidation with high sulfur deposition tolerance 钒作为LaFeO3钙钛矿“低温”H2S催化氧化的优良助剂，具有较高的耐硫沉积性

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-03-05 Epub Date: 2026-01-30 DOI: 10.1016/j.apcata.2026.120812

Fan Zhou , Xun Tao , Haoyuan Wang , Songling Guo , Luhang Jiao , Yifan Zhang , Yuying Wang , Xinlei Yu , Lu Ding , Fenglian Zhang , Yunfei Gao , Fuchen Wang

In this work, we discovered that V can be a superior promote in LaFeO₃ perovskite for H₂S selective catalytic oxidation (SCO) with high sulfur deposition tolerance and high activity at low temperature. The characterization results show that the nominal LaFe_0.8V_0.2O_3±δ is mainly composed of LaFeO₃/LaVO₄ with a small amount of V-doped LaFeO₃. The H₂S conversion can reach 99.6 % at 150 °C for LaFe_0.8V_0.2O_3±δ, which is much higher than LaFeO₃ (38.7 %). After 10 h of stability test, the H₂S conversion remained at 87.5 %. V doping can reduce the formation energy of oxygen vacancies, thereby increasing the content of oxygen vacancies. Besides, the addition of V interferes with the growth process of LaFeO₃ grains, hinders the aggregation and growth of nanoparticles, and greatly increases the specific surface area of the catalyst. Besides, V^5 + can accelerate the formation of active sites Fe³⁺ through the redox equilibrium reaction V⁵⁺ + Fe²⁺→V⁴⁺ + Fe³⁺, leading to synergistic effect between Fe and V. This study provides important progress for low-temperature H₂S catalytic oxidation catalysts with high sulfur deposition tolerance.

在这项工作中，我们发现V可以作为LaFeO3钙钛矿中H2S选择性催化氧化（SCO）的优良促进剂，具有高的耐硫沉积性和低温高活性。表征结果表明，标称LaFe0.8V0.2O3±δ主要由LaFeO3/LaVO4和少量v掺杂的LaFeO3组成。LaFe0.8V0.2O3±δ在150℃时H2S转化率可达99.6 %，远高于LaFeO3（38.7 %）。经过10 h的稳定性试验，H2S转化率保持在87.5 %。V掺杂可以降低氧空位的形成能，从而增加氧空位的含量。此外，V的加入干扰了LaFeO3晶粒的生长过程，阻碍了纳米颗粒的聚集和生长，大大增加了催化剂的比表面积。此外，V5 +可以通过氧化还原平衡反应V5+ + Fe2+→V4+ + Fe3+加速活性位点Fe3+的形成，使Fe和v之间产生协同效应。本研究为高耐硫沉积低温H2S催化氧化催化剂的研究提供了重要进展。

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引用次数: 0

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

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-03-05 Epub Date: 2026-01-20 DOI: 10.1016/j.apcata.2026.120796

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

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

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

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引用次数: 0

Simultaneous charge separation and defect passivation of perovskite by hydrogen-bonded organic framework for selective toluene photooxidation 氢键有机骨架在选择性甲苯光氧化中钙钛矿的同时电荷分离和缺陷钝化

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-03-05 Epub Date: 2026-01-27 DOI: 10.1016/j.apcata.2026.120810

Wei-Fan Shao , Bing-Hao Wang , Xiong Wang , Sheng Tian , Hui-Juan Wang , Xing-Sheng Hu , Chao Peng , Jin-Xin Li , Yang Li , Lang Chen , Shuang-Feng Yin

Efficient separation and migration of photogenerated carriers remains pivotal yet challenging for advancing photocatalytic performance. To address this bottleneck, we construct an intimately coupled hydrogen-bonded organic framework (HOF)-perovskite (MA₃Bi₂Br₉, MABB) heterojunction, where augmented built-in electric field (IEF) intensity enables directed accelerated carrier transfer. Benefiting from the interfacial compressive strain induced by lattice distortion, reinforced interfacial coupling interactions achieved in the optimized HOF-MABB-100. This system demonstrates exceptional performance in selective toluene photooxidation, with benzaldehyde production rate reaching 11,350 μmol g⁻¹ h⁻¹ and selectivity up 84 %. Simultaneously, HOF passivates the surface defects of MABB and thereby enhancing its stability by retaining 93 % of its catalytic activity after 4 successive cycles. This work validates the immense potential of HOF as a coupling module for designing high-performance lead-free perovskite photocatalysts.

光生成载体的高效分离和迁移仍然是提高光催化性能的关键和挑战。为了解决这一瓶颈，我们构建了一个紧密耦合的氢键有机框架(HOF)-钙钛矿（MA3Bi2Br9, mab）异质结，其中增强的内置电场（IEF）强度可以实现定向加速载流子转移。利用晶格畸变引起的界面压缩应变，优化后的HOF-MABB-100实现了增强的界面耦合作用。该体系在选择性甲苯光氧化中表现出优异的性能，苯甲醛的产率可达11,350 μmol g−1 h−1，选择性提高了84% %。同时，HOF钝化了MABB的表面缺陷，从而提高了其稳定性，在连续4次循环后保持了93 %的催化活性。这项工作验证了HOF作为设计高性能无铅钙钛矿光催化剂的耦合模块的巨大潜力。

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引用次数: 0