Applied Catalysis A: General最新文献_第4页

Acid-base bifunctional porous organic polymers as efficient catalysts for oil shale upgrading 酸碱双功能多孔有机聚合物作为油页岩提质的高效催化剂

IF 4.7 2区化学

Applied Catalysis A: General Pub Date : 2025-04-18 DOI: 10.1016/j.apcata.2025.120298

Xinbo Wang , Pengcheng Ma , Cong Yu , Junjie Bian , Xianglong Meng

引用次数: 0

Surface potential charge modulation and sequential etching strategies for optimizing SAPO-34 catalysts in the MTO process: Mechanistic insights into catalytic performance 在MTO过程中优化SAPO-34催化剂的表面电位电荷调制和顺序蚀刻策略：对催化性能的机理见解

IF 4.7 2区化学

Applied Catalysis A: General Pub Date : 2025-04-16 DOI: 10.1016/j.apcata.2025.120290

Hossein Mozafari Khalafbadam, Jafar Towfighi Darian, Masoud Safari Yazd

{"title":"Surface potential charge modulation and sequential etching strategies for optimizing SAPO-34 catalysts in the MTO process: Mechanistic insights into catalytic performance","authors":"Hossein Mozafari Khalafbadam, Jafar Towfighi Darian, Masoud Safari Yazd","doi":"10.1016/j.apcata.2025.120290","DOIUrl":"10.1016/j.apcata.2025.120290","url":null,"abstract":"<div><div>The methanol-to-olefins (MTO) process over SAPO-34 catalysts is significantly influenced by surface potential charge, affecting methanol adsorption, intermediate spillover, and coke formation. This study investigates the catalytic performance and mechanistic behavior of SAPO-34 catalysts modified through acidic (SP34-A), basic (SP34-B), and sequential acid-base (SP34-AB) etching, with the unmodified SAPO-34 (SP34-P) serving as a reference. The impact of surface potential charge on catalyst performance was examined using molecular dynamics (MD) simulations, NH<sub>3</sub>-TPD acidity measurements, and zeta potential analysis. The results reveal that a highly negative surface charge (SP34-A, −67 mV) intensifies methanol adsorption but limits spillover efficiency, promoting formaldehyde accumulation and increasing coke deposition, ultimately reducing catalyst lifetime. In contrast, a positive surface charge (SP34-B, +22 mV) enhances spillover and moderates adsorption strength, reducing coke formation and extending catalyst stability. The sequential acid-base etched catalyst (SP34-AB, +16.9 mV) achieves a well-balanced surface charge, optimizing methanol adsorption, spillover behavior, and diffusion efficiency. This balance minimizes secondary reactions, extends catalyst lifetime (586 min, 1.63 times longer than SP34-P), and improves light olefin selectivity (88.82 %), demonstrating the superior catalytic performance of SP34-AB. Structural and textural analysis further confirms that hierarchical porosity, induced via sequential etching, enhances mass transfer and mitigates diffusion limitations, preventing excessive coke formation. These findings establish surface potential charge as a critical parameter in SAPO-34 catalyst design, highlighting sequential acid-base etching as an effective modification strategy to enhance MTO efficiency and catalyst longevity.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"700 ","pages":"Article 120290"},"PeriodicalIF":4.7,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143838330","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

Oxidative conversion of cyclohexane to olefins on hexagonal boron nitride 六方氮化硼催化环己烷氧化转化烯烃的研究

IF 4.7 2区化学

Applied Catalysis A: General Pub Date : 2025-04-15 DOI: 10.1016/j.apcata.2025.120289

Wenru Li , Peiling Zhang , Jianjun Liu , Xin Li , Shaolong Wan , Shuai Wang , Yong Wang , Jingdong Lin

{"title":"Oxidative conversion of cyclohexane to olefins on hexagonal boron nitride","authors":"Wenru Li , Peiling Zhang , Jianjun Liu , Xin Li , Shaolong Wan , Shuai Wang , Yong Wang , Jingdong Lin","doi":"10.1016/j.apcata.2025.120289","DOIUrl":"10.1016/j.apcata.2025.120289","url":null,"abstract":"<div><div>The oxidative conversion of cyclohexane (OCC) to valuable olefins presents an innovative strategy for efficient utilization, overcoming its inherent resistance to traditional cracking methods. This study demonstrates the superior performance of hexagonal boron nitride (<em>h</em>-BN) in OCC, especially mitigating deep oxidation and dehydrogenation to achieve high olefin selectivity. At 550°C, with 32.5 % cyclohexane conversion, cyclohexene selectivity reaches 49.1 % and open-ring alkenes account for 20.1 %. The reaction is driven by gas-phase free radical mechanism, where higher reaction temperature and alkyl-oxygen ratio favor forming open-ring alkenes while maintaining high cyclohexene selectivity. The weak adsorption of olefins on <em>h</em>-BN and the suppression of deep oxidation and dehydrogenation through radical-mediated pathways are crucial for its exceptional performance. This approach effectively minimizes further oxidation and dehydrogenation of radicals and olefins, enhancing olefin selectivity. These findings provide a promising pathway for efficient cyclohexane utilization and advance the understanding of <em>h</em>-BN’s catalytic role in alkane oxidation process.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"700 ","pages":"Article 120289"},"PeriodicalIF":4.7,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143850068","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

Optimizing Mn/SiO2 catalyst for additive - free epoxidation of long - chain α -olefins in air 优化长链α -烯烃在空气中无添加剂环氧化的Mn/SiO2催化剂

IF 4.7 2区化学

Applied Catalysis A: General Pub Date : 2025-04-14 DOI: 10.1016/j.apcata.2025.120288

Fangchao Wang , Rui Liu , Hongyi Cui , Ali Ramazani , Ali Morsali , Guoying Zhang

{"title":"Optimizing Mn/SiO2 catalyst for additive - free epoxidation of long - chain α -olefins in air","authors":"Fangchao Wang , Rui Liu , Hongyi Cui , Ali Ramazani , Ali Morsali , Guoying Zhang","doi":"10.1016/j.apcata.2025.120288","DOIUrl":"10.1016/j.apcata.2025.120288","url":null,"abstract":"<div><div>The epoxidation of long-chain α-olefins presents a significant challenge in synthetic chemistry, particularly when employing molecular oxygen from air as the sole oxidant under additive-free conditions. In this study, we demonstrate that manganese supported on mesoporous silica (Mn/MSN) effectively catalyzes the aerobic epoxidation of long-chain α-olefins without requiring initiators or sacrificial agents. Mechanistic investigations reveal a synergistic interplay between Mn(II) and Mn(III) species, which facilitates the selective cleavage the peroxo bonds (O–O) in alkyl hydroperoxide intermediates. Strategic incorporation of iron and zirconium into the Mn/MSN framework modulates the manganese oxidation states, enriching the Mn(II)/Mn(III) ratio and achieving a remarkable space-time yield of up to 200 mol <sub>epoxide</sub> mol⁻¹<sub>Mn</sub> h⁻¹ . Radical trapping experiments combined with high-resolution mass spectrometry corroborate the formation of allyl carbon-centered and alkoxy radical intermediates during the reaction. This work provides a feasible strategy for long-chain α-olefin aerobic epoxidation without any additives.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"700 ","pages":"Article 120288"},"PeriodicalIF":4.7,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143838328","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

An alternative photochemical water oxidation pathway driven by halide ions as electron relay 卤化物离子作为电子继电器驱动的另一种光化学水氧化途径

IF 4.7 2区化学

Applied Catalysis A: General Pub Date : 2025-04-14 DOI: 10.1016/j.apcata.2025.120287

Chaowei Peng, Miao Shui, Haorui Wang, Hongfei Liu

引用次数: 0

CuZnAl embedded silicoaluminate catalyst promotion for the hydrogenation of carbon dioxide to dimethyl ether CuZnAl包埋硅铝酸盐催化剂促进二氧化碳加氢制二甲醚

IF 4.7 2区化学

Applied Catalysis A: General Pub Date : 2025-04-14 DOI: 10.1016/j.apcata.2025.120286

Yifan Wei , Jingyi Liu , Hanbo Li , Xian Zhang , Ying Zhang , Jiangong Yang , Mingpei Wang , Zhen Liu , Zifeng Yan

{"title":"CuZnAl embedded silicoaluminate catalyst promotion for the hydrogenation of carbon dioxide to dimethyl ether","authors":"Yifan Wei , Jingyi Liu , Hanbo Li , Xian Zhang , Ying Zhang , Jiangong Yang , Mingpei Wang , Zhen Liu , Zifeng Yan","doi":"10.1016/j.apcata.2025.120286","DOIUrl":"10.1016/j.apcata.2025.120286","url":null,"abstract":"<div><div>The resource utilization of CO<sub>2</sub> serves as a feasible method for emission reduction and the establishment of an artificial carbon cycle. This study primarily focuses on the direct synthesis of dimethyl ether (DME) from the hydrogenation of CO<sub>2</sub>. We have prepared bifunctional catalysts with metal oxides embedded in amorphous silicon-aluminum by an improved Stöber method. By precisely adjusting the Si/Al molar ratio and the CTAB/Si molar ratio in the synthesis precursor solution, structural characteristics and acid properties of the catalyst could be effectively regulated. The results indicated that compared to Cu/ZnO/Al<sub>2</sub>O<sub>3</sub>, the catalyst significantly enhanced the selectivity of DME and methanol (MeOH), reduced the selectivity of CO with a moderate conversion rate of CO<sub>2</sub>. The highest DME selectivity of 37.94 % was achieved at an Si/Al ratio of 8, with the total selectivity for methanol and DME reaching 52.96 %. The addition of cetyltrimethylammonium bromide (CTAB) increased the proportion of Brønsted acid sites and medium-strong acid sites, thereby enhancing methanol dehydration and suppressing the reverse water-gas shift reaction. The optimal selectivity for DME of 43 % was obtained over catalyst prepared with a CTAB/Si molar ratio of 0.1. This study provides a new strategy for the structural design of bifunctional catalysts for CO<sub>2</sub> hydrogenation.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"700 ","pages":"Article 120286"},"PeriodicalIF":4.7,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143838329","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

Melamine paraformaldehyde polymer as an excellent support for hydroformylations of various alkenes 三聚氰胺多聚甲醛聚合物作为各种烯烃氢甲酰化的优良载体

IF 4.7 2区化学

Applied Catalysis A: General Pub Date : 2025-04-12 DOI: 10.1016/j.apcata.2025.120281

Hanuman G. Kachgunde , Mariyamuthu Mariyaselvakumar , Lakhya Jyoti Konwar , Ankush V. Biradar

{"title":"Melamine paraformaldehyde polymer as an excellent support for hydroformylations of various alkenes","authors":"Hanuman G. Kachgunde , Mariyamuthu Mariyaselvakumar , Lakhya Jyoti Konwar , Ankush V. Biradar","doi":"10.1016/j.apcata.2025.120281","DOIUrl":"10.1016/j.apcata.2025.120281","url":null,"abstract":"<div><div>Aldehydes are a vital class of fine chemicals, widely utilized as intermediates in drug synthesis, as well as in the production of fragrances and flavors. In industrial settings, aldehydes are predominantly synthesized through hydroformylation reactions. Numerous phosphorus-containing homogeneous and heterogeneous ligands or supports have demonstrated catalytic activity in this process. In this study, we synthesized a rhodium-modified, melamine-paraformaldehyde polymer-based heterogeneous catalyst by condensation followed by a hydrothermal method. The amine groups in the polymer effectively anchored the rhodium, resulting in well-dispersed Rh nanoparticles on the PMF support. The absence of FTIR bands at 2053 and 2143cm<sup>-1</sup> confirmed the dissociation of Rh-complex. The HR-TEM identified the presence of ultrasmall Rh nanoparticles ( Avg. 2.9nm) on the polymer. The synthesized catalyst demonstrated excellent hydroformylation activity, achieving over 99% styrene conversion with 95% selectivity toward aldehyde products under optimized conditions and maintained performance over four cycles. Rh-PMF<sub>H</sub> catalyst showed high TON and TOF- 12,302, 2,050h<sup>-1,</sup> respectively. In addition, the catalyst showed excellent activity for a broad substrate scope.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"700 ","pages":"Article 120281"},"PeriodicalIF":4.7,"publicationDate":"2025-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143838332","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

Polyoxometalates as catalyst precursors for reverse water gas shift 多金属氧酸盐作为水气反移催化剂前驱体

IF 4.7 2区化学

Applied Catalysis A: General Pub Date : 2025-04-11 DOI: 10.1016/j.apcata.2025.120285

Asma M.O. Aldajani , Mounib Bahri , Elena F. Kozhevnikova , Ivan V. Kozhevnikov

{"title":"Polyoxometalates as catalyst precursors for reverse water gas shift","authors":"Asma M.O. Aldajani , Mounib Bahri , Elena F. Kozhevnikova , Ivan V. Kozhevnikov","doi":"10.1016/j.apcata.2025.120285","DOIUrl":"10.1016/j.apcata.2025.120285","url":null,"abstract":"<div><div>The reverse water gas shift (RWGS) was studied in the presence of catalysts based on Keggin-type polyoxometalates (POMs) such as heteropoly acids H<sub>3</sub>PMo<sub>12</sub>O<sub>40</sub> and H<sub>3</sub>PW<sub>12</sub>O<sub>40</sub> and their Co(II) and Ni(II) salts. Under reaction conditions, molybdenum POMs decomposed to form Mo oxide species, which exhibited high activity, selectivity and resistance to deactivation in the RWGS reaction. The catalysts formed from H<sub>3</sub>PMo<sub>12</sub>O<sub>40</sub> supported on SiO<sub>2</sub>, TiO<sub>2</sub> and γ-Al<sub>2</sub>O<sub>3</sub> produced CO with 100 % selectivity at 31–33 % CO<sub>2</sub> conversion at 600 °C and a CO<sub>2</sub>:H<sub>2</sub> molar ratio of 1:1 (cf. 39 % equilibrium conversion). H<sub>3</sub>PMo<sub>12</sub>O<sub>40</sub>/SiO<sub>2</sub> was more active than MoO<sub>3</sub>/SiO<sub>2</sub> with the same Mo loading, revealing a phosphorus enhancement effect on the activity of molybdenum species. This effect can be attributed to the influence of phosphate on the dispersion of the Mo oxide active phase. This is supported by STEM, which shows different morphologies of Mo oxide species in H<sub>3</sub>PMo<sub>12</sub>O<sub>40</sub>/SiO<sub>2</sub> and MoO<sub>3</sub>/SiO<sub>2</sub> catalysts. Chemical looping and H<sub>2</sub>-TPR of fresh and spent Mo catalysts show that the reaction occurs through the redox mechanism involving the reduction of Mo(VI) oxide species to Mo(IV) with H<sub>2</sub>, followed by reoxidation of Mo(IV) with CO<sub>2</sub> to form CO (reverse Mars–van Krevelen mechanism). Contrary to the Mo catalysts, tungsten POMs, exhibited no RWGS activity, which can be attributed to their resistance to reduction.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"699 ","pages":"Article 120285"},"PeriodicalIF":4.7,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143824524","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

Hierarchical porous S-1 zeolite supported Pt catalyst for catalytic oxidation of various VOCs at low temperature with strong water resistance and excellent stability 层次化多孔S-1沸石负载Pt催化剂在低温下催化氧化多种VOCs，具有较强的耐水性和优异的稳定性

IF 4.7 2区化学

Applied Catalysis A: General Pub Date : 2025-04-10 DOI: 10.1016/j.apcata.2025.120284

Kaifeng Sun , Fanzhe Kong , Xinru Gong , Yijun Shi , Dingfeng Jin , Hongxiao Jin , Xiaolin Guo , Renxian Zhou

{"title":"Hierarchical porous S-1 zeolite supported Pt catalyst for catalytic oxidation of various VOCs at low temperature with strong water resistance and excellent stability","authors":"Kaifeng Sun , Fanzhe Kong , Xinru Gong , Yijun Shi , Dingfeng Jin , Hongxiao Jin , Xiaolin Guo , Renxian Zhou","doi":"10.1016/j.apcata.2025.120284","DOIUrl":"10.1016/j.apcata.2025.120284","url":null,"abstract":"<div><div>The high mass transfer resistance of reactants and products limits the catalytic process of Silicalite-1 (S-1) based catalysts for volatile organic compounds (VOCs) oxidation. In the present work, Pt/S-1 catalysts with hierarchical pore structure were prepared with different concentrations of organic alkali TPAOH. The Pt/S-1–0.1 catalyst pretreated with 0.1 mol/L tetrapropyl ammonium hydroxide (TPAOH) has excellent VOCs catalytic oxidation activity for various types of VOCs including benzene, n-hexane, toluene, xylene, propane and propylene. The proper concentration of organic alkali pretreatment enhanced the interaction between Pt nanoparticles and the surface of zeolites, thus promoting the dispersion and anchoring of Pt on the surface of zeolites. The high dispersion of Pt nanoparticles with high proportion of Pt<sup>0</sup> species benefits the catalytic oxidation of VOCs at low temperature. In addition, due to the hydrophobic nature of S-1 zeolite, Pt/S-1–0.1 catalyst shows strong water resistance and excellent stability, which is suitable for catalytic oxidation of VOCs under high-water vapor content.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"699 ","pages":"Article 120284"},"PeriodicalIF":4.7,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143824525","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

Ammonia borane-promoted surface reconstruction of copper oxide catalysts for efficient catalytic hydrogen production from hydrolysis 氨硼烷促进氧化铜催化剂的表面重构，用于高效催化水解制氢

IF 4.7 2区化学

Applied Catalysis A: General Pub Date : 2025-04-10 DOI: 10.1016/j.apcata.2025.120283

Chenyang Wang, Yuchun Wang, Yiyan Bai, Wei Zhang, Zhaorong Liu

{"title":"Ammonia borane-promoted surface reconstruction of copper oxide catalysts for efficient catalytic hydrogen production from hydrolysis","authors":"Chenyang Wang, Yuchun Wang, Yiyan Bai, Wei Zhang, Zhaorong Liu","doi":"10.1016/j.apcata.2025.120283","DOIUrl":"10.1016/j.apcata.2025.120283","url":null,"abstract":"<div><div>During hydrogen production by hydrolysis of ammonia borane (AB), transition metal oxides act as active sites in the catalyst and can help to achieve rapid and large-scale release of hydrogen, but its catalytic mechanism is still under discussion. We developed a Cu<sub>2</sub>O/CuO catalyst with precisely controlled valence states and identified the fundamental source of the catalytic activity of oxides. The successive changes in the Cu valence state content of Cu<sub>2</sub>O/CuO resulted in a volcano-like trend of the catalyst activity, with the optimal hydrogen production rate from hydrolysis reaching 378.01 mL·g<sup>−1</sup>·min<sup>−1</sup>. The characterization of the catalysts after combined use revealed that AB prompted the catalyst surface to reconstruct during the catalytic process, forming a Cu/Cu<sub>2</sub>O heterostructure. This study established, for the first time, the structure-activity relationship between the valence state of copper and its catalytic activity, providing a theoretical basis for the construction of copper-based catalysts for AB hydrolysis.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"699 ","pages":"Article 120283"},"PeriodicalIF":4.7,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143826337","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