Journal of Catalysis最新文献_第8页

Effective coupling of aliphatic primary amines to imines on Cu-doped WO3 photocatalyst under aerobic and anaerobic conditions 在好氧和厌氧条件下，脂肪族伯胺与亚胺在cu掺杂WO3光催化剂上的有效偶联

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-03-19 DOI: 10.1016/j.jcat.2025.116091

Zhizhu Yue , Yonghe Yu , Tianjun Hu , Ying Wang , Yuhong Chang , Wenwen Chen , Linjuan Pei , Jianfeng Jia

{"title":"Effective coupling of aliphatic primary amines to imines on Cu-doped WO3 photocatalyst under aerobic and anaerobic conditions","authors":"Zhizhu Yue , Yonghe Yu , Tianjun Hu , Ying Wang , Yuhong Chang , Wenwen Chen , Linjuan Pei , Jianfeng Jia","doi":"10.1016/j.jcat.2025.116091","DOIUrl":"10.1016/j.jcat.2025.116091","url":null,"abstract":"<div><div>Imide, a key intermediate in organic synthesis, has extensive applications. The oxidative coupling of aliphatic primary amines to imines is challenging due to low reactivity. In this study, under visible light irradiation, Cu-doped WO<sub>3</sub> photocatalysts significantly enhanced the oxidative performance of aliphatic primary amines in both aerobic and anaerobic conditions, achieving imine yields of 94 % and 80 %, respectively. This performance is substantially superior to that of undoped WO<sub>3</sub> and is broadly applicable to both aliphatic and aromatic amines. This improvement is attributed to the Cu doping, which not only enhances the light absorption capabilities of WO<sub>3</sub> but also introduces oxygen vacancies that increase the adsorption and activation capacity for reactant molecules, altering the material’s band structure, enhancing light responsiveness, and promoting effective carrier separation. Additionally, radical quenching experiments confirmed the roles of holes and singlet oxygen in the aerobic reactions, while under anaerobic conditions, holes (h<sup>+</sup>) and electrons (e<sup>-</sup>) dominate, leading to high conversion rates and selectivity, as well as the detection of hydrogen. These findings provide important insights for designing efficient, non-precious metal-doped photocatalysts and advance the understanding of amine oxidative coupling.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"446 ","pages":"Article 116091"},"PeriodicalIF":6.5,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660687","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Identification and evolution of active sites in isomorphously substituted Fe-ZSM-5 catalysts for methane dehydroaromatization (MDA) 同形取代Fe-ZSM-5甲烷脱氢芳构化催化剂活性位点的鉴定与演化

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-03-19 DOI: 10.1016/j.jcat.2025.116090

Xinrui Zhang , Jordy Ramos-Yataco , Shan Jiang , Qingheng Lai , Selim Alayoglu , Jeffery T. Miller , Tobin J. Marks , Justin M. Notestein

{"title":"Identification and evolution of active sites in isomorphously substituted Fe-ZSM-5 catalysts for methane dehydroaromatization (MDA)","authors":"Xinrui Zhang , Jordy Ramos-Yataco , Shan Jiang , Qingheng Lai , Selim Alayoglu , Jeffery T. Miller , Tobin J. Marks , Justin M. Notestein","doi":"10.1016/j.jcat.2025.116090","DOIUrl":"10.1016/j.jcat.2025.116090","url":null,"abstract":"<div><div>Methane dehydroaromatization (MDA) enables the catalytic conversion of methane into aromatics, mainly benzene, along with hydrogen, in a single-step process under non-oxidative conditions. In this study, we prepared a series of isomorphously substituted Fe-ZSM-5 catalysts with exclusively isolated or low-oligomerized sites up to 3.2 % Fe weight loading by adding ethylenediaminetetraacetic acid (EDTA) to the crystallization gel. These catalysts exhibit no induction/activation period and a significantly higher maximum product yield compared to Fe/ZSM-5 catalysts prepared by the incipient wetness impregnation method and containing extensively aggregated FeOx. This investigation focuses on the evolution of Fe sites during the post-synthetic treatments. Most importantly, we demonstrate the quantitative relation between Fe site isolation and catalytic activity, proving that isolated or low-oligomerized Fe species at the exchange sites formed during post-synthetic treatment are the active sites for methane activation.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"446 ","pages":"Article 116090"},"PeriodicalIF":6.5,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143661092","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Synergistic effect of single atoms and clusters on boosting activity of TiO2-supported Pd catalysts towards total furfural hydrogenation 单原子和团簇对tio2负载Pd催化剂全糠醛加氢活性的协同作用

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-03-18 DOI: 10.1016/j.jcat.2025.116083

Jin Gu , Hao Zhang , Miao Guo , Yanming Hu

{"title":"Synergistic effect of single atoms and clusters on boosting activity of TiO2-supported Pd catalysts towards total furfural hydrogenation","authors":"Jin Gu , Hao Zhang , Miao Guo , Yanming Hu","doi":"10.1016/j.jcat.2025.116083","DOIUrl":"10.1016/j.jcat.2025.116083","url":null,"abstract":"<div><div>Total furfural (FAL) hydrogenation to the industrially valuable tetrahydrofurfuryl alcohol (THFOL) involves the cascade hydrogenation of the formyl and furanic groups. However, supported metal catalysts are generally confronted with low activity, especially under mild conditions. Herein, we present a highly active Pd catalyst supported on TiO<sub>2</sub> with a Pd loading of 0.2 wt% (0.2Pd/TiO<sub>2</sub>) for the efficient one-pot conversion of FAL to THFOL. Under mild conditions (25 °C, 60 bar H<sub>2</sub>), 0.2Pd/TiO<sub>2</sub> achieves 90 % FAL conversion and 96 % selectivity to THFOL, outperforming the conventional high-Pd-content catalysts (e.g. 5 wt%Pd/TiO<sub>2</sub>) and most reported catalysts. Detailed characterization and kinetic investigations reveal that the exceptional performance stems from the synergistic interplay between Pd single atoms and nanoclusters on the 0.2Pd/TiO<sub>2</sub> catalyst. Furthermore, kinetic studies highlight the crucial role of H<sub>2</sub>O in promoting the desired reaction pathway. Impressively, 0.2Pd/TiO<sub>2</sub> demonstrates excellent stability, the activity and selectivity remain nearly identical even over seven consecutive reaction cycles. Moreover, the catalyst exhibits broad applicability, effectively hydrogenating various furanic compounds to the corresponding saturated products. This study provides key insights into the rational design of highly efficient and selective catalysts for tandem hydrogenation reactions.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"446 ","pages":"Article 116083"},"PeriodicalIF":6.5,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654005","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Engineering surface defect active sites in SnS2 nanosheets with electron-donating groups for efficient photoelectrochemical water splitting 具有供电子基团的SnS2纳米片表面缺陷活性位点工程用于高效光电化学水分解

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-03-18 DOI: 10.1016/j.jcat.2025.116087

Meng Wang , Jianli Chen , Chengming Zhang , Huihui Ding , HuanHuan Wu , Xiang Li , Shuangshuang Huai , Zhi Tang , Xiaoli Zhao , Hewen Liu , Xiufang Wang

{"title":"Engineering surface defect active sites in SnS2 nanosheets with electron-donating groups for efficient photoelectrochemical water splitting","authors":"Meng Wang , Jianli Chen , Chengming Zhang , Huihui Ding , HuanHuan Wu , Xiang Li , Shuangshuang Huai , Zhi Tang , Xiaoli Zhao , Hewen Liu , Xiufang Wang","doi":"10.1016/j.jcat.2025.116087","DOIUrl":"10.1016/j.jcat.2025.116087","url":null,"abstract":"<div><div>Lack of surface charge and poor carrier separation efficiency limit the photoelectrochemical (PEC) water splitting performance. Therefore, enhancing the charge density around the surface-active sites is an important strategy to boost the PEC performance. Herein, an in-situ strategy to construct surface S vacancies (S<sub>v</sub>) and introduce hydroxyl groups (–OH) on the SnS<sub>2</sub> photoanode is designed, and its PEC water splitting activity has significantly improved, reaching a maximum photocurrent density of 1.44 mA·cm<sup>−2</sup> at 1.23 V<sub>RHE</sub>, which is 8.47 times greater than in terms of pure SnS<sub>2</sub>, and the onset potential has an obvious negative shift. Complete theoretical simulations and detailed experimental tests show that the –OH groups, as strong electron donors, transfer charge to the S vacancy sites and increase the surface charge density. Effective separation and transport of the photoinduced carriers are achieved. The ability of S<sub>v</sub> active sites to activate and stabilize H<sub>2</sub>O molecules and reaction intermediates is also effectively improved to ensure the smooth progress of the water oxidation reaction. This work offers a novel approach for the synthesis of effective photoanodes by modifying surface defect active sites with electron donor groups.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"446 ","pages":"Article 116087"},"PeriodicalIF":6.5,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654004","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Improved photocatalytic hydrogen production with the π-d conjugation between amino groups in COFs and CoS2, along with the S-scheme heterojunction COFs和CoS2中氨基之间的π-d偶联以及s -图式异质结改善了光催化制氢

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-03-17 DOI: 10.1016/j.jcat.2025.116086

Xinwan Zhao , Minjun Lei , Xiaoli Ma , Youji Li , Zhiliang Jin

{"title":"Improved photocatalytic hydrogen production with the π-d conjugation between amino groups in COFs and CoS2, along with the S-scheme heterojunction","authors":"Xinwan Zhao , Minjun Lei , Xiaoli Ma , Youji Li , Zhiliang Jin","doi":"10.1016/j.jcat.2025.116086","DOIUrl":"10.1016/j.jcat.2025.116086","url":null,"abstract":"<div><div>Covalent organic frameworks are promising polymer semiconductors for solar-driven hydrogen production. However, rapid charge recombination and low surface reaction kinetics currently limit their photocatalytic performance. A two-dimensional Schiff base TaTp-covalent organic framework loaded with CoS<sub>2</sub> was synthesized via a one-pot solid-state thermal method in this study, and an inorganic-organic S-scheme heterojunction CoS<sub>2</sub>/TaTp-COF composite material was thereby constructed. When the CoS<sub>2</sub> loading reached 11 wt%, an optimal photocatalytic H<sub>2</sub> evolution rate was demonstrated by the composite, achieving an apparent quantum efficiency of 5.91 % at 500 nm. This notable improvement can be ascribed to the π-d conjugation effect occurring at the heterojunction interface. This phenomenon facilitates effective charge separation and transfer, consequently boosting the redox capabilities. Both experimental results and theoretical calculations confirmed the successful formation of the S-scheme heterojunction and elucidated the underlying charge transfer mechanism. This research not only provides new insights into COF-based photocatalytic hydrogen evolution but also offers valuable strategies for designing heterojunction catalysts.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"446 ","pages":"Article 116086"},"PeriodicalIF":6.5,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640014","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Visible-light-mediated oxidation of saturated C(sp3)-H bonds over [W10O32]4−-POMOFs [W10O32]4−-POMOFs上饱和C(sp3)-H键的可见光氧化

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-03-17 DOI: 10.1016/j.jcat.2025.116088

Yanjie Lv , Dianxiang Peng , Wenxi Zhang , Jing Sun , Huiying Sun , Xin Wang , Xiao Li , Mingwei Ma , Zhongmin Su

{"title":"Visible-light-mediated oxidation of saturated C(sp3)-H bonds over [W10O32]4−-POMOFs","authors":"Yanjie Lv , Dianxiang Peng , Wenxi Zhang , Jing Sun , Huiying Sun , Xin Wang , Xiao Li , Mingwei Ma , Zhongmin Su","doi":"10.1016/j.jcat.2025.116088","DOIUrl":"10.1016/j.jcat.2025.116088","url":null,"abstract":"<div><div>How to efficiently oxidize cyclohexane through C(sp<sup>3</sup>)-H bond activation has been a major challenge in industry. In this paper, a new polyoxometalate based metal–organic frameworks, named as <strong>CUST-906</strong> is designed and synthesized with the formula of Cu(bix)<sub>2</sub>(W<sub>10</sub>O<sub>32</sub>)<sub>0.5</sub>, (bix = 1,4-Bis(imidazol-1-ylmethyl)benzene). Decatungstate as photosensitizer, <strong>CUST-906</strong> can catalyze the oxidation reaction of cyclohexane under visible light with mild reaction conditions, the conversion rate can reach high as 33.4 %, which is far higher than that of the industrial level (less than 4 %), and the selectivity of cyclohexanol and cyclohexanone (KA oil) is greater than 99 %. <strong>CUST-906</strong> exhibits excellent light absorption ability and photogenerated carrier separation ability under visible light, which endows <strong>CUST-906</strong> strong catalytic oxidation capacity and good recyclability for the oxidation reaction of cyclohexane. We delve into the discussion the activation of C(sp<sup>3</sup>)-H bonds by the hydrogen atom transfer (HAT) process of decatungstate, which synergies with the central metal to achieve the photocatalytic oxidation process via ·O<sub>2</sub><sup>−</sup> and h<sup>+</sup>. This work provides a new idea for heterogeneous catalysis of cyclohexane oxidation.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"446 ","pages":"Article 116088"},"PeriodicalIF":6.5,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640413","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Inhibition of NH3-SCR over Cu-CHA at high partial pressures of water: Measurements and DFT-based kinetic modeling 高分压下NH3-SCR对Cu-CHA的抑制作用：测量和基于dft的动力学建模

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-03-17 DOI: 10.1016/j.jcat.2025.116071

Shivangi Singh , Yingxin Feng , Ton V.W. Janssens , Henrik Grönbeck

{"title":"Inhibition of NH3-SCR over Cu-CHA at high partial pressures of water: Measurements and DFT-based kinetic modeling","authors":"Shivangi Singh , Yingxin Feng , Ton V.W. Janssens , Henrik Grönbeck","doi":"10.1016/j.jcat.2025.116071","DOIUrl":"10.1016/j.jcat.2025.116071","url":null,"abstract":"<div><div>Cu-exchanged chabazite (Cu-CHA) is a widely applied catalyst for selective catalytic reduction of nitrogen oxides in oxygen excess. The application of Cu-CHA to exhaust from H<sub>2</sub>-fueled engines depends on the behavior of this material at high partial pressures of water. We have performed flow-reactor measurements, which show that the NO<span><math><msub><mrow></mrow><mrow><mi>x</mi></mrow></msub></math></span> conversion at 200 °C over a Cu-CHA (3.2 wt% Cu, Si/Al=6.7) catalyst decreases with increasing partial pressures of water from 2 to 25%. Simultaneously, the apparent reaction order in water decreases from <span><math><mrow><mo>−</mo><mn>0</mn><mo>.</mo><mn>17</mn></mrow></math></span> to <span><math><mrow><mo>−</mo><mn>1</mn><mo>.</mo><mn>18</mn></mrow></math></span>, following the simple empirical equation <span><math><mrow><mo>−</mo><mn>3</mn><mo>.</mo><mn>43</mn><mspace></mspace><msup><mrow><mrow><mo>(</mo><msub><mrow><mi>p</mi></mrow><mrow><msub><mrow><mi>H</mi></mrow><mrow><mn>2</mn></mrow></msub><mi>O</mi></mrow></msub><mo>/</mo><msup><mrow><mi>p</mi></mrow><mrow><mo>∘</mo></mrow></msup><mo>)</mo></mrow></mrow><mrow><mn>0</mn><mo>.</mo><mn>76</mn></mrow></msup></mrow></math></span>. The experimental results are corroborated with DFT-based microkinetic modeling. The DFT calculations show that H<sub>2</sub>O competes with NO adsorption on the Cu-sites and hinders the reaction. The kinetic model describes accurately the inhibiting effect of water after minor adjustments to the computed Gibbs free energies of water adsorption.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"446 ","pages":"Article 116071"},"PeriodicalIF":6.5,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640418","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Tailoring microenvironments of metal-enzyme cascade catalysts for efficient DKR reaction of chiral amine 手性胺DKR高效反应金属-酶级联催化剂微环境的定制

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-03-16 DOI: 10.1016/j.jcat.2025.116079

Mengyu Li , Wei Zhuang , Xia Meng , Wenxia Zhang , Keke Zhang , Zhenfu Wang

{"title":"Tailoring microenvironments of metal-enzyme cascade catalysts for efficient DKR reaction of chiral amine","authors":"Mengyu Li , Wei Zhuang , Xia Meng , Wenxia Zhang , Keke Zhang , Zhenfu Wang","doi":"10.1016/j.jcat.2025.116079","DOIUrl":"10.1016/j.jcat.2025.116079","url":null,"abstract":"<div><div>Metal-enzyme integrated catalysts combine the high selectivity of enzyme catalysts with the broad substrate spectrum of metal catalysts and offer tremendous possibilities for chemoenzymatic cascade processes. However, the rational design of microenvironments in nanostructures that make metals and enzymes compatible for efficient activity still remains challenging. In this report, a nanocomposite catalyst was fabricated by integrating ultrafine Pd nanoparticles (Pd NPs) and <em>Candida antarctica</em> lipase B (CALB) on the hydrophobic polydopamine-coated SiO<sub>2</sub> (SP) to enhance the compatibility of enzyme-metal catalysts. In detail, Pd NPs were in situ reduced by PDA on the SP surface, and the obtained SP-loaded Pd (Pd/SP) was hydrophobically modified by octadecyltrimethoxysilane for the subsequent adsorption immobilization of CALB to prepare the integrated catalyst, CALB/mPd/SP. The hydrophobic PDA coating on SiO<sub>2</sub> not only stabilized the loaded ultrasmall Pd nanoparticles but also facilitated the activation of the immobilized lipase, which helped to improve the cascade catalytic efficiency of CALB/mPd/SP. Afterward, CALB/mPd/SP was used in a one-pot dynamic kinetic resolution (DKR) reaction of α-phenylethylamine with high conversion (>99 %), selectivity (93.9 %), and ee<sub>p</sub> (>99 %). After 25 days of storage and 5 h of sonication, CALB/mPd/SP exhibited no significant reduction in the DKR catalytic activity. This study proposed a simple and sustainable method for the preparation of enzyme-metal cascade catalysts to enhance their stability and achieve significantly increased activity through interfacial microenvironmental modulation.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"446 ","pages":"Article 116079"},"PeriodicalIF":6.5,"publicationDate":"2025-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635655","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Adsorption coupled metal/anion/oxide structure for synergistic synthesizing solketal from glycerol 吸附偶联金属/阴离子/氧化物结构协同合成甘油溶胶

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-03-16 DOI: 10.1016/j.jcat.2025.116084

Lumei Wang , Dezhang Ren , Junyu Lang , Kangqi Gao , Xiao Du , Yong Yang , Zhibao Huo

{"title":"Adsorption coupled metal/anion/oxide structure for synergistic synthesizing solketal from glycerol","authors":"Lumei Wang , Dezhang Ren , Junyu Lang , Kangqi Gao , Xiao Du , Yong Yang , Zhibao Huo","doi":"10.1016/j.jcat.2025.116084","DOIUrl":"10.1016/j.jcat.2025.116084","url":null,"abstract":"<div><div>Although homogeneous acid catalysts have been widely utilized in the production of solketal from glycerol, a significant aspect of the biodiesel industry, challenges remain, including the high corrosiveness of the catalysts and their excessive usage. In this study, a composite material of wCo(NO<sub>3</sub>)<sub>2</sub>/γ-Al<sub>2</sub>O<sub>3</sub> was synthesized through an adsorption–desorption approach based on wet impregnation, achieving a Co(II) loading of only 1.8 wt%, which demonstrated a solketal yield of 84 % at 80 °C, significantly outperforming the catalytic activity of Co(NO<sub>3</sub>)<sub>2</sub>. Even when the amount of Co(NO<sub>3</sub>)<sub>2</sub> was increased to 22-fold that of the Co(II) content in wCo(NO<sub>3</sub>)<sub>2</sub>/γ-Al<sub>2</sub>O<sub>3</sub>, the solketal yield only reached 67 %. Through systematic physicochemical characterization and theoretical calculations, it is revealed that Co(NO<sub>3</sub>)<sub>2</sub> can be uniformly dispersed in an amorphous state on the surface of γ-Al<sub>2</sub>O<sub>3</sub>. Furthermore, γ-Al<sub>2</sub>O<sub>3</sub> facilitates a reduction in the orbital binding energy of Co and N within Co(NO<sub>3</sub>)<sub>2</sub>. The synergistic effects of Co(II), NO<sub>3</sub><sup>−</sup>, and γ-Al<sub>2</sub>O<sub>3</sub> contribute to decreasing the rate-determining energy of the ketalization reaction, thereby promoting the dehydration reactions of glycerol and acetone. Furthermore, this strategy is equally applicable to other soluble Co, Ni, and Cu salts, demonstrating universality. This method effectively reduces the usage of metal salts in the solketal synthesis process, enhancing the acid catalytic activity of the metal salts, providing an adsorption–desorption approach based on wet impregnation for the development of low-dose, highly active, and low-corrosive acid catalytic materials.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"446 ","pages":"Article 116084"},"PeriodicalIF":6.5,"publicationDate":"2025-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635552","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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

Acidity-enhanced Al-MCM-41 synthesized by phase transformation of MWW-type zeolites for the liquid-phase alkylation of lignin-derived phenolic compounds 通过 MWW 型沸石相变合成的酸性增强型 Al-MCM-41 用于木质素衍生酚类化合物的液相烷基化反应

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2025-03-15 DOI: 10.1016/j.jcat.2025.116081

Ping He , Huawei Geng , Lin Li , Qisong Yi , Lu Lin , Zhifeng Liu , Yuanshuai Liu , Valentin Valtchev

{"title":"Acidity-enhanced Al-MCM-41 synthesized by phase transformation of MWW-type zeolites for the liquid-phase alkylation of lignin-derived phenolic compounds","authors":"Ping He , Huawei Geng , Lin Li , Qisong Yi , Lu Lin , Zhifeng Liu , Yuanshuai Liu , Valentin Valtchev","doi":"10.1016/j.jcat.2025.116081","DOIUrl":"10.1016/j.jcat.2025.116081","url":null,"abstract":"<div><div>Solid acidic Al-MCM-41 materials are characterized by a high specific surface area and well-ordered hexagonally shaped mesopores. However, their relatively weak acidity compared to microporous zeolites significantly limits their practical applications in industrial catalytic reactions, particularly in upgrading biomass-derived organic feedstock that involves reactions with bulky molecules. Herein, we report a novel synthesis route for preparing acidity-enhanced Al-MCM-41 through the phase transformation of MWW-type zeolite precursors. The phase transformation approach markedly facilitates the incorporation of aluminum species into the MCM-41 framework, leading to strong Brønsted acidity of the resultant Al-MCM-41-T samples, as evidenced by comprehensive characterizations including <sup>29</sup>Si and <sup>27</sup>Al MAS NMR, NH<sub>3</sub>-TPD, and Py-IR. Owing to the enhanced acidity and its large pore structures, the as-prepared Al-MCM-41-T-15 sample (with Si/Al = 15) exhibited superior activity and selectivity toward C-alkylated products in both liquid-phase phenol-cyclohexanol and 4-cyclohexylphenol (4-CHP)-cyclohexene alkylation reactions compared the commercial Al-MCM-41-C with a similar Si/Al ratio. These findings afford an effective approach for preparing acidity-enhanced mesoporous solid acids, which hold significant potential for catalyzing lignin-derived bio-oils.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"446 ","pages":"Article 116081"},"PeriodicalIF":6.5,"publicationDate":"2025-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143631329","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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