Pub Date : 2026-01-14DOI: 10.1016/j.mcat.2026.115716
Yulin Qi, Yao Yao, Chunxiu Liu, Mingliang Shi, Shan-Yong Chen, Yue Qi, Na Wang
Herein, we have developed a visible-light-induced formylation system without an exogenous photocatalyst for synthesizing indole derivatives. Notably, this system operates under ambient air, utilizing readily available aqueous formaldehyde as the formyl source. Mechanistic studies reveal that the reaction involves the in-situ formylation of a Mannich-type intermediate from the indole, formaldehyde and amine, followed by photochemical oxidation and hydrolysis. This simple, mild, metal-free, and photocatalyst-free protocol enables the synthesis of a diverse array of C-3 formylated indoles, demonstrating good functional group compatibility and broad potential for late-stage functionalization.
{"title":"Photocatalyst-free and simple photooxidative C-3 formylation of indoles with formaldehyde","authors":"Yulin Qi, Yao Yao, Chunxiu Liu, Mingliang Shi, Shan-Yong Chen, Yue Qi, Na Wang","doi":"10.1016/j.mcat.2026.115716","DOIUrl":"10.1016/j.mcat.2026.115716","url":null,"abstract":"<div><div>Herein, we have developed a visible-light-induced formylation system without an exogenous photocatalyst for synthesizing indole derivatives. Notably, this system operates under ambient air, utilizing readily available aqueous formaldehyde as the formyl source. Mechanistic studies reveal that the reaction involves the in-situ formylation of a Mannich-type intermediate from the indole, formaldehyde and amine, followed by photochemical oxidation and hydrolysis. This simple, mild, metal-free, and photocatalyst-free protocol enables the synthesis of a diverse array of C-3 formylated indoles, demonstrating good functional group compatibility and broad potential for late-stage functionalization.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"592 ","pages":"Article 115716"},"PeriodicalIF":4.9,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145975557","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}
Pub Date : 2026-01-13DOI: 10.1016/j.mcat.2026.115719
Ming Su , Xiaoli Ma , Jian Ma , Zhiliang Jin
A ZnSe/ZnIn2S4 composite heterojunction was constructed, and its structure, optoelectronic properties, and hydrogen evolution mechanism were systematically investigated. The synergistic interaction significantly enhances light absorption and charge separation. The ZZ-50 sample achieves a high hydrogen evolution rate of 1174.97 μmol∙g-1∙h-1 with excellent stability. XPS and electrochemical analyses reveal electron transfer from ZnSe to ZnIn2S4, forming a built-in electric field that suppresses recombination. DFT calculations confirm suitable bandgap alignment. Combined experimental and theoretical results elucidate the mechanism of directional electron migration, thereby enhancing photocatalytic performance. This study provides new insights for designing efficient visible-light-responsive materials.
{"title":"Construction of microsphere-nanoflower structured ZnSe/ZnIn2S4 heterojunction for enhanced photocatalytic hydrogen evolution and mechanistic study","authors":"Ming Su , Xiaoli Ma , Jian Ma , Zhiliang Jin","doi":"10.1016/j.mcat.2026.115719","DOIUrl":"10.1016/j.mcat.2026.115719","url":null,"abstract":"<div><div>A ZnSe/ZnIn<sub>2</sub>S<sub>4</sub> composite heterojunction was constructed, and its structure, optoelectronic properties, and hydrogen evolution mechanism were systematically investigated. The synergistic interaction significantly enhances light absorption and charge separation. The ZZ-50 sample achieves a high hydrogen evolution rate of 1174.97 μmol∙g<sup>-1</sup>∙h<sup>-1</sup> with excellent stability. XPS and electrochemical analyses reveal electron transfer from ZnSe to ZnIn<sub>2</sub>S<sub>4</sub>, forming a built-in electric field that suppresses recombination. DFT calculations confirm suitable bandgap alignment. Combined experimental and theoretical results elucidate the mechanism of directional electron migration, thereby enhancing photocatalytic performance. This study provides new insights for designing efficient visible-light-responsive materials.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"592 ","pages":"Article 115719"},"PeriodicalIF":4.9,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145975558","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}
Pub Date : 2026-01-12DOI: 10.1016/j.mcat.2026.115704
Xinru Li , Jianfeng Zheng , Hongqiang Yang , Ying Shi , Qixiong Hou , Yan Cui , Zhanggen Huang
The hydrolysis of carbonyl sulfide (COS) to hydrogen sulfide (H2S) is of paramount importance in blast furnace gas (BFG) purification. In practical applications, the H2S/COS ratio fluctuates due to variations in ironmaking raw materials and operational conditions, while the inevitable presence of oxygen (O2) leads to catalyst deactivation, severely compromising the hydrolysis process. In this study, K-modified NaY zeolite catalysts were prepared via impregnation, and the effects of temperature, H2S/COS ratio, and O2 concentration on COS hydrolysis performance were systematically investigated. Experimental results demonstrate that the NaY zeolite loaded with 10% KOH exhibits good adaptability to fluctuations in the H2S/COS ratio and possesses excellent oxygen resistance. Optimal catalytic performance was achieved at 100 °C with an H2S:COS ratio of 1:3 and an O₂ concentration of 0.3%, under which the COS hydrolysis efficiency exceeded 92% for 12 hours. Characterization results indicate that weak and medium-strength basic sites synergistically regulate adsorption/desorption behaviors and the local acid-base microenvironment. This synergy prevents issues such as insufficient reactant adsorption or hindered product desorption caused by the dominance of a single type of basic site, thereby significantly optimizing the COS hydrolysis performance. This study proposes an effective solution for COS hydrolysis and provides fundamental data for further catalyst optimization and industrial application.
{"title":"Modulation of basic sites for enhanced COS hydrolysis performance over NaY zeolite catalysts","authors":"Xinru Li , Jianfeng Zheng , Hongqiang Yang , Ying Shi , Qixiong Hou , Yan Cui , Zhanggen Huang","doi":"10.1016/j.mcat.2026.115704","DOIUrl":"10.1016/j.mcat.2026.115704","url":null,"abstract":"<div><div>The hydrolysis of carbonyl sulfide (COS) to hydrogen sulfide (H<sub>2</sub>S) is of paramount importance in blast furnace gas (BFG) purification. In practical applications, the H<sub>2</sub>S/COS ratio fluctuates due to variations in ironmaking raw materials and operational conditions, while the inevitable presence of oxygen (O<sub>2</sub>) leads to catalyst deactivation, severely compromising the hydrolysis process. In this study, K-modified NaY zeolite catalysts were prepared via impregnation, and the effects of temperature, H<sub>2</sub>S/COS ratio, and O<sub>2</sub> concentration on COS hydrolysis performance were systematically investigated. Experimental results demonstrate that the NaY zeolite loaded with 10% KOH exhibits good adaptability to fluctuations in the H<sub>2</sub>S/COS ratio and possesses excellent oxygen resistance. Optimal catalytic performance was achieved at 100 °C with an H<sub>2</sub>S:COS ratio of 1:3 and an O₂ concentration of 0.3%, under which the COS hydrolysis efficiency exceeded 92% for 12 hours. Characterization results indicate that weak and medium-strength basic sites synergistically regulate adsorption/desorption behaviors and the local acid-base microenvironment. This synergy prevents issues such as insufficient reactant adsorption or hindered product desorption caused by the dominance of a single type of basic site, thereby significantly optimizing the COS hydrolysis performance. This study proposes an effective solution for COS hydrolysis and provides fundamental data for further catalyst optimization and industrial application.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"592 ","pages":"Article 115704"},"PeriodicalIF":4.9,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145947968","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}
Pub Date : 2026-01-11DOI: 10.1016/j.mcat.2026.115714
Neslisah Ulus , Volkan Sahin , Marwen Elkamel , Ozge Yuksel Orhan , Hulya Yavuz Ersan
The increasing demand for sustainable energy has made hydrogen important as a clean energy carrier. Formic acid (FA), a biomass-derived liquid, is a promising approach for hydrogen storage media due to its high hydrogen content. High-efficiency FA dehydrogenation is a challenging goal, particularly due to difficulties in catalyst design, such as the agglomeration of subnanometric metal nanostructures within porous support materials. In this study, hierarchical MFI zeolites were synthesized via seed-assisted crystallization using a multiple quaternary ammonium-based structure-guiding agent (SDA), and different types of metals (Pd, Co, Ni, and Cu) were confined via ethylenediamine-ligand protection. This integrated synthesis approach ensured the homogeneous positioning of metal nanosites (MNS) within the zeolite lattice structure, creating thermally stabilized nanosheets. The resulting catalysts were tested in FA dehydrogenation reactions, proving that this synthesis approach is effective in designing active and stable catalytic systems. Among these catalysts, Pd(0.2)@hMFI achieved the highest catalytic activity under optimized reaction conditions, obtaining a conversion frequency (TOF) of 1801.25 h-1. The presence of secondary mesoporosity within the hierarchical structure improved mass transfer while enhancing the distribution of homogeneous subnanometric metal sites and their reusability. The catalyst retained >90 % of its initial activity after 5 cycles, proving the stability and cost-effectiveness of hierarchical zeolite-based systems with embedded subnanometric active sites for energy applications. To support and improve the experimental data, machine learning models were developed to predict hydrogen production depending on catalyst type, temperature, time, and FA/SF ratio parameters. The XGBoost model achieved the highest accuracy (RMSE = 0.46 and R2 = 0.998) among the tested models, demonstrating the effectiveness of ensemble learning for reliable H2 prediction.
{"title":"Metal nanosites-confined hierarchical zeolite for enhanced formic acid dehydrogenation","authors":"Neslisah Ulus , Volkan Sahin , Marwen Elkamel , Ozge Yuksel Orhan , Hulya Yavuz Ersan","doi":"10.1016/j.mcat.2026.115714","DOIUrl":"10.1016/j.mcat.2026.115714","url":null,"abstract":"<div><div>The increasing demand for sustainable energy has made hydrogen important as a clean energy carrier. Formic acid (FA), a biomass-derived liquid, is a promising approach for hydrogen storage media due to its high hydrogen content. High-efficiency FA dehydrogenation is a challenging goal, particularly due to difficulties in catalyst design, such as the agglomeration of subnanometric metal nanostructures within porous support materials. In this study, hierarchical MFI zeolites were synthesized via seed-assisted crystallization using a multiple quaternary ammonium-based structure-guiding agent (SDA), and different types of metals (Pd, Co, Ni, and Cu) were confined via ethylenediamine-ligand protection. This integrated synthesis approach ensured the homogeneous positioning of metal nanosites (MNS) within the zeolite lattice structure, creating thermally stabilized nanosheets. The resulting catalysts were tested in FA dehydrogenation reactions, proving that this synthesis approach is effective in designing active and stable catalytic systems. Among these catalysts, Pd(0.2)@hMFI achieved the highest catalytic activity under optimized reaction conditions, obtaining a conversion frequency (TOF) of 1801.25 h<sup>-1</sup>. The presence of secondary mesoporosity within the hierarchical structure improved mass transfer while enhancing the distribution of homogeneous subnanometric metal sites and their reusability. The catalyst retained >90 % of its initial activity after 5 cycles, proving the stability and cost-effectiveness of hierarchical zeolite-based systems with embedded subnanometric active sites for energy applications. To support and improve the experimental data, machine learning models were developed to predict hydrogen production depending on catalyst type, temperature, time, and FA/SF ratio parameters. The XGBoost model achieved the highest accuracy (RMSE = 0.46 and R<sup>2</sup> = 0.998) among the tested models, demonstrating the effectiveness of ensemble learning for reliable H<sub>2</sub> prediction.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115714"},"PeriodicalIF":4.9,"publicationDate":"2026-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145973716","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}
Pub Date : 2026-01-10DOI: 10.1016/j.mcat.2026.115713
Ohud Almutairi , Amal Alasmari , Rawan Al-Faze , Elena F. Kozhevnikova , Ivan V. Kozhevnikov
Dehydration of 1-butanol primarily produces n-butene isomers, key olefinic feedstocks in the chemical industry. The reaction was studied in the gas phase using silica-supported Keggin heteropoly acids (HPAs) H3PW12O40 (HPW) and H4SiW12O40 (HSiW) as solid acid catalysts. The HPA catalysts were benchmarked against zeolites, such as H-ZSM-5, H-Mordenite and HY, the established catalysts for alcohol dehydration. The HPA catalysts were found to exhibit significantly higher activity and performance stability than zeolites. 25% HPW/SiO2 and 25% HSiW/SiO2 catalysts produced n-butene isomers at 130 °C with 99% selectivity (1-butene (8.4%) < cis-2-butene (30.3%) < trans-2-butene (61.3%)) at 99% conversion of 1-butanol and maintained stable performance for at least 24 h. The HPA-catalysed dehydration of 1-butanol followed the Langmuir rate equation, becoming zero-order in 1-butanol at partial pressures ≥1 kPa. A positive correlation between catalyst acid strength and reaction turnover rates was established. Evidence was provided that the reaction proceeds via a surface-type mechanism through an E2 elimination pathway.
{"title":"Silica-supported heteropoly acids as catalysts for low-temperature dehydration of 1-butanol in the gas phase: Application and mechanistic insight","authors":"Ohud Almutairi , Amal Alasmari , Rawan Al-Faze , Elena F. Kozhevnikova , Ivan V. Kozhevnikov","doi":"10.1016/j.mcat.2026.115713","DOIUrl":"10.1016/j.mcat.2026.115713","url":null,"abstract":"<div><div>Dehydration of 1-butanol primarily produces n-butene isomers, key olefinic feedstocks in the chemical industry. The reaction was studied in the gas phase using silica-supported Keggin heteropoly acids (HPAs) H<sub>3</sub>PW<sub>12</sub>O<sub>40</sub> (HPW) and H<sub>4</sub>SiW<sub>12</sub>O<sub>40</sub> (HSiW) as solid acid catalysts. The HPA catalysts were benchmarked against zeolites, such as H-ZSM-5, H-Mordenite and HY, the established catalysts for alcohol dehydration. The HPA catalysts were found to exhibit significantly higher activity and performance stability than zeolites. 25% HPW/SiO<sub>2</sub> and 25% HSiW/SiO<sub>2</sub> catalysts produced n-butene isomers at 130 °C with 99% selectivity (1-butene (8.4%) < cis-2-butene (30.3%) < trans-2-butene (61.3%)) at 99% conversion of 1-butanol and maintained stable performance for at least 24 h. The HPA-catalysed dehydration of 1-butanol followed the Langmuir rate equation, becoming zero-order in 1-butanol at partial pressures ≥1 kPa. A positive correlation between catalyst acid strength and reaction turnover rates was established. Evidence was provided that the reaction proceeds via a surface-type mechanism through an E2 elimination pathway.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115713"},"PeriodicalIF":4.9,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922433","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}
Pub Date : 2026-01-10DOI: 10.1016/j.mcat.2026.115712
Shuaidong Li , Laixi Zou , Hui Li , Yaozong Liu , Xinyi Wang
With rising palladium prices, palladium-free catalysis is critical for cost reduction in PCB electroless copper plating. This study used DFT to investigate the reaction mechanism of colloidal Ag-catalyzed electroless copper plating. Four reaction mechanisms (a-d) are designed for Ag-catalyzed formaldehyde-reduced copper electroless plating in alkaline solution. Adsorption behaviors of H, HCOO⁻, HCOOH, CH2O22⁻, CH2(OH)O⁻ and CH(OH)2O⁻ are systematically analyzed. Results showed these species spontaneously adsorb on the Ag(111) to form stable structures. Thermodynamic analysis identified OH⁻-mediated CH2(OH)O⁻ transformation as the optimal single-step pathway, corresponding to mechanism d with 1.59 eV activation barrier. Electronic structure analysis confirms Ag's potential as a high-efficiency catalyst. This work provides theoretical guidance for developing Ag-catalyzed electroless copper plating processes.
{"title":"DFT study on the interface reaction mechanism of colloidal silver-catalyzed electroless copper plating process","authors":"Shuaidong Li , Laixi Zou , Hui Li , Yaozong Liu , Xinyi Wang","doi":"10.1016/j.mcat.2026.115712","DOIUrl":"10.1016/j.mcat.2026.115712","url":null,"abstract":"<div><div>With rising palladium prices, palladium-free catalysis is critical for cost reduction in PCB electroless copper plating. This study used DFT to investigate the reaction mechanism of colloidal Ag-catalyzed electroless copper plating. Four reaction mechanisms (a-d) are designed for Ag-catalyzed formaldehyde-reduced copper electroless plating in alkaline solution. Adsorption behaviors of H, HCOO⁻, HCOOH, CH<sub>2</sub>O<sub>2</sub><sup>2⁻</sup>, CH<sub>2</sub>(OH)O⁻ and CH(OH)<sub>2</sub>O⁻ are systematically analyzed. Results showed these species spontaneously adsorb on the Ag(111) to form stable structures. Thermodynamic analysis identified OH⁻-mediated CH<sub>2</sub>(OH)O⁻ transformation as the optimal single-step pathway, corresponding to mechanism d with 1.59 eV activation barrier. Electronic structure analysis confirms Ag's potential as a high-efficiency catalyst. This work provides theoretical guidance for developing Ag-catalyzed electroless copper plating processes.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115712"},"PeriodicalIF":4.9,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145973717","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}
Pub Date : 2026-01-10DOI: 10.1016/j.mcat.2026.115709
Li Xing , Yuhong Wang , Ke Lin , Wei Liu , Rui Cao , Lei Song
{"title":"Corrigendum to “CuOx/CoOx tandem catalyst for effectively reducing nitrate to ammonia” [Molecular Catalysis 579 (2025) 115056]","authors":"Li Xing , Yuhong Wang , Ke Lin , Wei Liu , Rui Cao , Lei Song","doi":"10.1016/j.mcat.2026.115709","DOIUrl":"10.1016/j.mcat.2026.115709","url":null,"abstract":"","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115709"},"PeriodicalIF":4.9,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145973715","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}
Pub Date : 2026-01-09DOI: 10.1016/j.mcat.2026.115711
Damir Nasokhov, Alexey Philippov, Nikolay Nesterov, Vera Pakharukova, Igor Prosvirin, Oleg Martyanov
The study aims to control the selectivity towards hydrodeoxygenation (HDO) products in the transfer hydrogenation of guaiacol and anisole by decelerating aromatic ring saturation, using isopropanol as a hydrogen donor. For this purpose, bifunctional Ni-Co catalysts were synthesized using an eco-friendly method based on coprecipitation in supercritical CO2. The bifunctionality of the bimetallic catalysts was achieved through the controlled replacement of some nickel with cobalt, a metal that is known to have lower activity in the saturation of aromatic rings. The peculiarities of the synthesized samples are high content of the active compound and monophasic bimetallic particles, which facilitates interaction between Ni and Co. It was observed that the rate of aromatic ring saturation decreased as nickel was substituted for cobalt in the catalyst. Simultaneously, the rate constants of anisole and guaiacol HDO responded differently to cobalt substitution. The hydrogenolysis of the COMe bond in guaiacol accelerated with higher Co content. In contrast, for anisole, the elimination of the same fragment, catalyzed by bimetallic catalysts, slowed down compared to the monometallic Ni sample. Importantly, the approach of slowing hydrodearomatization proved versatile, as this effect was observed for both anisole and guaiacol with an increase in Co content. Thus, this work demonstrates the design of catalysts capable of processing real lignin pyrolysis oil, which is rich in a diverse set of oxygenated molecules.
{"title":"Hydrodearomatization deceleration as a key factor of improved selectivity in transfer hydrogenation of phenolics over Ni-Co bifunctional catalysts","authors":"Damir Nasokhov, Alexey Philippov, Nikolay Nesterov, Vera Pakharukova, Igor Prosvirin, Oleg Martyanov","doi":"10.1016/j.mcat.2026.115711","DOIUrl":"10.1016/j.mcat.2026.115711","url":null,"abstract":"<div><div>The study aims to control the selectivity towards hydrodeoxygenation (HDO) products in the transfer hydrogenation of guaiacol and anisole by decelerating aromatic ring saturation, using isopropanol as a hydrogen donor. For this purpose, bifunctional Ni-Co catalysts were synthesized using an eco-friendly method based on coprecipitation in supercritical CO<sub>2</sub>. The bifunctionality of the bimetallic catalysts was achieved through the controlled replacement of some nickel with cobalt, a metal that is known to have lower activity in the saturation of aromatic rings. The peculiarities of the synthesized samples are high content of the active compound and monophasic bimetallic particles, which facilitates interaction between Ni and Co. It was observed that the rate of aromatic ring saturation decreased as nickel was substituted for cobalt in the catalyst. Simultaneously, the rate constants of anisole and guaiacol HDO responded differently to cobalt substitution. The hydrogenolysis of the C<img>OMe bond in guaiacol accelerated with higher Co content. In contrast, for anisole, the elimination of the same fragment, catalyzed by bimetallic catalysts, slowed down compared to the monometallic Ni sample. Importantly, the approach of slowing hydrodearomatization proved versatile, as this effect was observed for both anisole and guaiacol with an increase in Co content. Thus, this work demonstrates the design of catalysts capable of processing real lignin pyrolysis oil, which is rich in a diverse set of oxygenated molecules.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115711"},"PeriodicalIF":4.9,"publicationDate":"2026-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922432","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}
This study introduces a novel type of carbon-doped amorphous titanium dioxide material FA-TiO2. It is synthesized through the modification of ferulic acid (FA), which facilitates the formation of more abundant oxygen vacancies in amorphous titanium dioxide, thereby enhancing its photocatalytic nitrogen fixation capabilities. It has been established through a range of characterization techniques that the FA modification exerts a substantial influence on the electronic structure, surface properties and photocatalytic activity of the catalyst. Compared with amorphous titanium dioxide, the nitrogen fixation efficiency of FA-TiO2 is as high as 155.19 µmol g⁻¹ h⁻¹, which is 11.14 times faster than TiO2. Additionally, the 15N2 isotope experiment qualitatively identified the nitrogen source employed in ammonia synthesis throughout the nitrogen fixation process involving FA-TiO2. The results indicate that the synergistic regulation of the electronic structure by doped carbon atoms is a simple method for preparing oxygen-vacancy photocatalysts, and the amorphous FA-TiO2 photocatalyst prepared has high efficient photocatalytic activity for nitrogen fixation.
{"title":"High effectively fixing nitrogen by Carbon-doped amorphous TiO2 with abundant oxygen vacancies under visible light and normal pressure and temperature","authors":"Jingyi Qu, Zhexiao Zhu, Jiahui Lin, Xiaolu Xu, Yangben Chen, Xintong Li, Runze Guo, Hui Zheng","doi":"10.1016/j.mcat.2026.115705","DOIUrl":"10.1016/j.mcat.2026.115705","url":null,"abstract":"<div><div>This study introduces a novel type of carbon-doped amorphous titanium dioxide material FA-TiO<sub>2</sub>. It is synthesized through the modification of ferulic acid (FA), which facilitates the formation of more abundant oxygen vacancies in amorphous titanium dioxide, thereby enhancing its photocatalytic nitrogen fixation capabilities. It has been established through a range of characterization techniques that the FA modification exerts a substantial influence on the electronic structure, surface properties and photocatalytic activity of the catalyst. Compared with amorphous titanium dioxide, the nitrogen fixation efficiency of FA-TiO<sub>2</sub> is as high as 155.19 µmol g⁻¹ h⁻¹, which is 11.14 times faster than TiO<sub>2</sub>. Additionally, the <sup>15</sup>N<sub>2</sub> isotope experiment qualitatively identified the nitrogen source employed in ammonia synthesis throughout the nitrogen fixation process involving FA-TiO<sub>2</sub>. The results indicate that the synergistic regulation of the electronic structure by doped carbon atoms is a simple method for preparing oxygen-vacancy photocatalysts, and the amorphous FA-TiO<sub>2</sub> photocatalyst prepared has high efficient photocatalytic activity for nitrogen fixation.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115705"},"PeriodicalIF":4.9,"publicationDate":"2026-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922430","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}
Pub Date : 2026-01-09DOI: 10.1016/j.mcat.2026.115710
Tao Ye, Baocheng Zhou, Pengfei Sun, Xiaoping Dong, Sanchuan Yu
5-Hydroxymethyl-2-furan carboxylic acid (HMFCA) is an important raw material in the chemical and pharmaceutical industries. In this work, we developed a strategy to the utilization of fly ash resource to obtain CaA zeolite and employed as catalyst supports Au nanoparticles to obtain high catalytic performance for the oxidation of 5-hydroxymethylfurfural (HMF) to HMFCA using air as an oxidant. Herein, the catalyst was synthesized through cation-exchange and wet impregnation method. The composition, morphology, and structure of the as-prepared catalyst were characterized. The effects of surface chemistry, the amount of Au loading, catalyst dosage, reaction time and reaction temperature on catalytic performance for the selective oxidation of 5-HMF to HMFCA were systematically investigated. In particular, the optimal 1.0 wt% Au-CaA catalyst afforded a satisfactory HMFCA yield of 89.2% and selectively of 91.5% from HMF oxidation using air as the oxidant and KHCO3 as base in water at 80 °C. This excellent catalytic performance is not only attributed to the high charge density and total acidity of CaA zeolite, but also ascribe to the strong acid sites of support and high dispersion of Au nanoparticles, which promoted the activation of reactants and further improved HMFCA selectivity. Moreover, the relationship between structure (Au particle size, basicity within zeolites and Auδ+ species) and the yield of HMFCA was concretely established. Reaction mechanism analysis revealed the pathway and the formation of Auδ+ species on the as-prepared catalyst was the crucial step. This work may be potential platforms for the effective catalytic synthesis of sustainable value-added chemicals from biomass, and has pioneered new and environmentally friendly applications for the resource utilization of fly ash.
{"title":"Valorization of fly ash to Au/CaA zeolite catalyst for selective oxidation of HMF to HMFCA: A waste-to-wealth strategy","authors":"Tao Ye, Baocheng Zhou, Pengfei Sun, Xiaoping Dong, Sanchuan Yu","doi":"10.1016/j.mcat.2026.115710","DOIUrl":"10.1016/j.mcat.2026.115710","url":null,"abstract":"<div><div>5-Hydroxymethyl-2-furan carboxylic acid (HMFCA) is an important raw material in the chemical and pharmaceutical industries. In this work, we developed a strategy to the utilization of fly ash resource to obtain CaA zeolite and employed as catalyst supports Au nanoparticles to obtain high catalytic performance for the oxidation of 5-hydroxymethylfurfural (HMF) to HMFCA using air as an oxidant. Herein, the catalyst was synthesized through cation-exchange and wet impregnation method. The composition, morphology, and structure of the as-prepared catalyst were characterized. The effects of surface chemistry, the amount of Au loading, catalyst dosage, reaction time and reaction temperature on catalytic performance for the selective oxidation of 5-HMF to HMFCA were systematically investigated. In particular, the optimal 1.0 wt% Au-CaA catalyst afforded a satisfactory HMFCA yield of 89.2% and selectively of 91.5% from HMF oxidation using air as the oxidant and KHCO<sub>3</sub> as base in water at 80 °C. This excellent catalytic performance is not only attributed to the high charge density and total acidity of CaA zeolite, but also ascribe to the strong acid sites of support and high dispersion of Au nanoparticles, which promoted the activation of reactants and further improved HMFCA selectivity. Moreover, the relationship between structure (Au particle size, basicity within zeolites and Au<sup>δ+</sup> species) and the yield of HMFCA was concretely established. Reaction mechanism analysis revealed the pathway and the formation of Au<sup>δ+</sup> species on the as-prepared catalyst was the crucial step. This work may be potential platforms for the effective catalytic synthesis of sustainable value-added chemicals from biomass, and has pioneered new and environmentally friendly applications for the resource utilization of fly ash.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115710"},"PeriodicalIF":4.9,"publicationDate":"2026-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922429","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}
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