NbOPO4 supported TiO2 materials were demonstrated to be excellent catalysts for selective conversion of C6-carbohydrates to 5-hydroxymethylfurfural in an environmentally benign dimethyl carbonate-water solvent system. The materials presented high activity and excellent stability in sub-critical water conditions (upto 180 °C and 20 bar), enabling continuous 5-hydroxymethylfurfural production from highly concentrated sugars (35 wt% fructose, glucose and glucose:fructose mixtures) in a micro fixed-bed reactor. The high catalytic activity (6–27.3 KgHMFKgCat−1day−1) and good-to-excellent HMF selectivity (55–91 %) and exceptional hydrolytic stability and regenerability observed under process conditions was attributed to a highly crystalline NbOPO4 phase with Q2 and Q3 phosphates stabilized on a TiO2 framework with tunable acidity (0.11–0.52 mmolH+g−1 and Brønsted/Lewis ratio) and acidic strength comparable to bulk-NbOPO4. Furthermore, our experiments also revealed the importance of organic solvents in modulating catalyst acidic properties, particularly the strength of Brønsted acid sites which, in turn, influenced the HMF productivity.
{"title":"Environmentally benign and continuous 5-hydroxymethylfurfural (HMF) production from concentrated sugars over NbOPO4 supported TiO2 catalyst in a dimethyl carbonate-water biphasic system","authors":"Ganesh Govind Kadam , Satish Kumar Nayak , Ajaikumar Samikannu , Jyri-Pekka Mikkola , Lakhya Jyoti Konwar","doi":"10.1016/j.apcata.2024.120087","DOIUrl":"10.1016/j.apcata.2024.120087","url":null,"abstract":"<div><div>NbOPO<sub>4</sub> supported TiO<sub>2</sub> materials were demonstrated to be excellent catalysts for selective conversion of C6-carbohydrates to 5-hydroxymethylfurfural in an environmentally benign dimethyl carbonate-water solvent system. The materials presented high activity and excellent stability in sub-critical water conditions (upto 180 °C and 20 bar), enabling continuous 5-hydroxymethylfurfural production from highly concentrated sugars (35 wt% fructose, glucose and glucose:fructose mixtures) in a micro fixed-bed reactor. The high catalytic activity (6–27.3 Kg<sub>HMF</sub>Kg<sub>Cat</sub><sup>−1</sup>day<sup>−1</sup>) and good-to-excellent HMF selectivity (55–91 %) and exceptional hydrolytic stability and regenerability observed under process conditions was attributed to a highly crystalline NbOPO<sub>4</sub> phase with Q<sub>2</sub> and Q<sub>3</sub> phosphates stabilized on a TiO<sub>2</sub> framework with tunable acidity (0.11–0.52 mmol<sub>H</sub><sup>+</sup>g<sup>−1</sup> and Brønsted/Lewis ratio) and acidic strength comparable to bulk-NbOPO<sub>4</sub>. Furthermore, our experiments also revealed the importance of organic solvents in modulating catalyst acidic properties, particularly the strength of Brønsted acid sites which, in turn, influenced the HMF productivity.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"691 ","pages":"Article 120087"},"PeriodicalIF":4.7,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143135268","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 : 2025-02-05DOI: 10.1016/j.apcata.2024.120034
Mohammad Moniruzzaman , Lars C. Grabow , Michael P. Harold
Forced dynamic operation (FDO) of selective oxidation of propylene to acrolein is evaluated on a structured alumina foam coated with a mixed metal oxide catalyst (bismuth molybdate-based). Reactor experiments examine feed composition modulation as a strategy to increase the yield of acrolein. At lower temperatures, separating the oxidant (O2) and reductant (C3H6) enhances propylene conversion and acrolein selectivity. Variation in the reaction-regeneration switching amplitude and frequency gives a 40 % higher cycle-averaged acrolein yield compared to steady-state operation (SSO) for the same overall feed composition. The results suggest that FDO maintains a higher concentration of selective oxygen species during the propylene feed, while pre-oxidation of the catalyst maximizes the amount of selective oxygen species, leading to increased acrolein yield at the beginning of the reaction cycle. Experiments at lower temperature for both commercial promoted and in-house, unpromoted catalysts reveal both catalysts are most active and selective at their highest oxidation states.
{"title":"Forced dynamic operation of propylene selective oxidation to acrolein on bismuth-molybdate structured catalysts","authors":"Mohammad Moniruzzaman , Lars C. Grabow , Michael P. Harold","doi":"10.1016/j.apcata.2024.120034","DOIUrl":"10.1016/j.apcata.2024.120034","url":null,"abstract":"<div><div>Forced dynamic operation (FDO) of selective oxidation of propylene to acrolein is evaluated on a structured alumina foam coated with a mixed metal oxide catalyst (bismuth molybdate-based). Reactor experiments examine feed composition modulation as a strategy to increase the yield of acrolein. At lower temperatures, separating the oxidant (O<sub>2</sub>) and reductant (C<sub>3</sub>H<sub>6</sub>) enhances propylene conversion and acrolein selectivity. Variation in the reaction-regeneration switching amplitude and frequency gives a 40 % higher cycle-averaged acrolein yield compared to steady-state operation (SSO) for the same overall feed composition. The results suggest that FDO maintains a higher concentration of selective oxygen species during the propylene feed, while pre-oxidation of the catalyst maximizes the amount of selective oxygen species, leading to increased acrolein yield at the beginning of the reaction cycle. Experiments at lower temperature for both commercial promoted and in-house, unpromoted catalysts reveal both catalysts are most active and selective at their highest oxidation states.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"691 ","pages":"Article 120034"},"PeriodicalIF":4.7,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143135251","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 : 2025-02-05DOI: 10.1016/j.apcata.2024.120074
Ching Wei Low , Andrei Veksha , Rupendra Aryal , Wei Ping Chan , Grzegorz Lisak
The potential replaceability of a Ni catalyst supported on commercial α-Al2O3 (Ni/Al2O3) by Ni on biomass-derived char (Ni/Char), and Ni on spent fluid catalytic cracking catalyst (Ni/FCC) for steam reforming of biomass pyrolysis gas was investigated (14 h at 850°C, steam/carbon ratio = 5). The catalysts reformed 60–80 % of C2-C5 hydrocarbons, producing 2.7–4.1 mg min−1 of H2. The reforming activity of Ni/Al2O3 and Ni/FCC was higher compared to Ni/Char, indicating the beneficial role of metal oxide supports. The use of Al2O3 and FCC resulted in a lower thermo-oxidative stability of coke formed on Ni/Al2O3 and Ni/FCC compared to Ni/Char. Furthermore, the deposited Ni showed higher stability towards oxidation by steam into NiO in case of Al2O3 and FCC compared to char. According to reforming activity, H2 production rate, coking, and Ni oxidation of the catalysts, FCC has better prospects as an alternative support in a reforming catalyst than char.
{"title":"Catalytic reforming of biomass pyrolysis gas over Ni catalysts: Alumina, spent fluid catalytic cracking catalyst and char as supports","authors":"Ching Wei Low , Andrei Veksha , Rupendra Aryal , Wei Ping Chan , Grzegorz Lisak","doi":"10.1016/j.apcata.2024.120074","DOIUrl":"10.1016/j.apcata.2024.120074","url":null,"abstract":"<div><div>The potential replaceability of a Ni catalyst supported on commercial α-Al<sub>2</sub>O<sub>3</sub> (Ni/Al<sub>2</sub>O<sub>3</sub>) by Ni on biomass-derived char (Ni/Char), and Ni on spent fluid catalytic cracking catalyst (Ni/FCC) for steam reforming of biomass pyrolysis gas was investigated (14 h at 850°C, steam/carbon ratio = 5). The catalysts reformed 60–80 % of C<sub>2</sub>-C<sub>5</sub> hydrocarbons, producing 2.7–4.1 mg min<sup>−1</sup> of H<sub>2</sub>. The reforming activity of Ni/Al<sub>2</sub>O<sub>3</sub> and Ni/FCC was higher compared to Ni/Char, indicating the beneficial role of metal oxide supports. The use of Al<sub>2</sub>O<sub>3</sub> and FCC resulted in a lower thermo-oxidative stability of coke formed on Ni/Al<sub>2</sub>O<sub>3</sub> and Ni/FCC compared to Ni/Char. Furthermore, the deposited Ni showed higher stability towards oxidation by steam into NiO in case of Al<sub>2</sub>O<sub>3</sub> and FCC compared to char. According to reforming activity, H<sub>2</sub> production rate, coking, and Ni oxidation of the catalysts, FCC has better prospects as an alternative support in a reforming catalyst than char.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"691 ","pages":"Article 120074"},"PeriodicalIF":4.7,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143135052","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 : 2025-02-05DOI: 10.1016/j.apcata.2024.120033
N. Mora , E. Blanco , J. Seguel , J.N.Díaz de León , N. Escalona
In the present work, the promoter effect of nickel over rhenium-supported catalysts was studied for the valorization of bio-oil model compounds. The catalysts were characterized by X-ray diffraction, N2 adsorption isotherms at −196 °C, temperature programmed reduction, NH3-temperature programmed desorption, CO chemisorption, and X-ray photoelectron spectroscopy. The catalytic performance was evaluated in a batch reactor at 350 °C and 50 bar of H2. The characterization results show that two phenomena occur with the inclusion of Ni through post-impregnation: A higher exposure of rhenium phases and formation of ReC and metallic Re at higher Ni contents and an electronic transfer from Ni to Re. The catalysts were evaluated for the hydrodeoxygenation reaction (HDO) of guaiacol used as a bio-oil model compound. The most active catalysts were the Re-Ni(3 %)/AC and Re-Ni(5 %)/AC samples. Cyclohexanol and cyclohexane were the main products obtained from the hydrogenation of phenol promoted by the reduced rhenium species.
{"title":"Nickel promoter effect in rhenium catalysts for valorization of bio-oil model molecules","authors":"N. Mora , E. Blanco , J. Seguel , J.N.Díaz de León , N. Escalona","doi":"10.1016/j.apcata.2024.120033","DOIUrl":"10.1016/j.apcata.2024.120033","url":null,"abstract":"<div><div>In the present work, the promoter effect of nickel over rhenium-supported catalysts was studied for the valorization of bio-oil model compounds. The catalysts were characterized by X-ray diffraction, N<sub>2</sub> adsorption isotherms at −196 °C, temperature programmed reduction, NH<sub>3</sub>-temperature programmed desorption, CO chemisorption, and X-ray photoelectron spectroscopy. The catalytic performance was evaluated in a batch reactor at 350 °C and 50 bar of H<sub>2</sub>. The characterization results show that two phenomena occur with the inclusion of Ni through post-impregnation: A higher exposure of rhenium phases and formation of ReC and metallic Re at higher Ni contents and an electronic transfer from Ni to Re. The catalysts were evaluated for the hydrodeoxygenation reaction (HDO) of guaiacol used as a bio-oil model compound. The most active catalysts were the Re-Ni(3 %)/AC and Re-Ni(5 %)/AC samples. Cyclohexanol and cyclohexane were the main products obtained from the hydrogenation of phenol promoted by the reduced rhenium species.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"691 ","pages":"Article 120033"},"PeriodicalIF":4.7,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143135088","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}
SiO2-supported cesium phosphate (CsxP/SiO2, x = molar ratio of Cs/P) catalysts show promising catalytic performance for the vapor-phase transformation of 1,2-propanediol (1,2-PDO) to allyl alcohol (AAL). The formation of AAL proceeded via propylene oxide (PO) formation. Simultaneously, 1,2-PDO was also converted to propanal (PAL). The Cs/SiO2 without P mainly generated PO, and introducing P into Cs/SiO2 promoted the consecutive transformation of PO to AAL with the concurrent reduction of PAL selectivity. Several reaction parameters, such as reaction temperature, contact time, and the phosphate content influenced the catalytic activity and product distribution. A Cs1.4P/SiO2 catalyst with a phosphate content of 20 wt% exhibited 100 % 1,2-PDO conversion with the AAL selectivity of 77 % at 400 °C and a contact time of 1.67 h. The poisoning experiment using probe molecules reveals that basic sites are essential for the PO formation, while acid-base sites are important in the isomerization of PO to AAL.
{"title":"Vapor-phase dehydration of 1,2-propanediol to allyl alcohol over silica-supported cesium phosphate","authors":"Masafumi Morooka , Enggah Kurniawan , Junji Okamura , Yusei Nagamura , Yasuhiro Yamada , Satoshi Sato","doi":"10.1016/j.apcata.2024.120064","DOIUrl":"10.1016/j.apcata.2024.120064","url":null,"abstract":"<div><div>SiO<sub>2</sub>-supported cesium phosphate (Cs<sub><em>x</em></sub>P/SiO<sub>2</sub>, <em>x</em> = molar ratio of Cs/P) catalysts show promising catalytic performance for the vapor-phase transformation of 1,2-propanediol (1,2-PDO) to allyl alcohol (AAL). The formation of AAL proceeded <em>via</em> propylene oxide (PO) formation. Simultaneously, 1,2-PDO was also converted to propanal (PAL). The Cs/SiO<sub>2</sub> without P mainly generated PO, and introducing P into Cs/SiO<sub>2</sub> promoted the consecutive transformation of PO to AAL with the concurrent reduction of PAL selectivity. Several reaction parameters, such as reaction temperature, contact time, and the phosphate content influenced the catalytic activity and product distribution. A Cs<sub>1.4</sub>P/SiO<sub>2</sub> catalyst with a phosphate content of 20 wt% exhibited 100 % 1,2-PDO conversion with the AAL selectivity of 77 % at 400 °C and a contact time of 1.67 h. The poisoning experiment using probe molecules reveals that basic sites are essential for the PO formation, while acid-base sites are important in the isomerization of PO to AAL.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"691 ","pages":"Article 120064"},"PeriodicalIF":4.7,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143135252","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-05DOI: 10.1016/j.apcata.2024.120076
Jialiang Ke , Wenqian Fu , Lei Zhang , Chenglong Yuan , Tiandi Tang
A one-pot synthesis strategy for the Cu-containing Silicalite-1 (Cu@S-1-N) zeolite with Cu+ anchored in silanol nests was initially presented via using nitrilotriacetic acid (H3NTA) as a ligand. Introducing H3NTA guaranteed the formation of a copper-chelate in the form of [Cu(NTA)2]2- in the precursor solution, whose un-coordinated carboxylate ion may condensate with silicate during the crystallization process, leading to the innumerable highly active and stable Cu+ species in the final Cu@S-1-N zeolite. In the model benzaldehyde ammoxidation reaction, the highly dispersed and electron-deficient Cu+ species in the Cu@S-1-N catalyst was more active and stable than the Cu2+ species in the Cu/S-1-N catalyst prepared by the incipient wetness impregnation method. The Cu+ species preferentially chemisorbed benzaldehyde, activating its carbonyl carbon for nucleophilic attack by the amino group from the decomposition of ammonium carbonate and subsequent toward the benzonitrile formation.
{"title":"One-step synthesized Cu-containing Silicalite-1 zeolite using Cu-NTA complex for the selective ammoxidation reaction","authors":"Jialiang Ke , Wenqian Fu , Lei Zhang , Chenglong Yuan , Tiandi Tang","doi":"10.1016/j.apcata.2024.120076","DOIUrl":"10.1016/j.apcata.2024.120076","url":null,"abstract":"<div><div>A one-pot synthesis strategy for the Cu-containing Silicalite-1 (Cu@S-1-N) zeolite with Cu<sup>+</sup> anchored in silanol nests was initially presented via using nitrilotriacetic acid (H<sub>3</sub>NTA) as a ligand. Introducing H<sub>3</sub>NTA guaranteed the formation of a copper-chelate in the form of [Cu(NTA)<sub>2</sub>]<sup>2-</sup> in the precursor solution, whose un-coordinated carboxylate ion may condensate with silicate during the crystallization process, leading to the innumerable highly active and stable Cu<sup>+</sup> species in the final Cu@S-1-N zeolite. In the model benzaldehyde ammoxidation reaction, the highly dispersed and electron-deficient Cu<sup>+</sup> species in the Cu@S-1-N catalyst was more active and stable than the Cu<sup>2+</sup> species in the Cu/S-1-N catalyst prepared by the incipient wetness impregnation method. The Cu<sup>+</sup> species preferentially chemisorbed benzaldehyde, activating its carbonyl carbon for nucleophilic attack by the amino group from the decomposition of ammonium carbonate and subsequent toward the benzonitrile formation.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"691 ","pages":"Article 120076"},"PeriodicalIF":4.7,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143135265","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}
Using lignin to produce valuable chemicals can help reduce reliance on fossil fuels. The NiO catalyst prepared by alcohol/water co-precipitation method showed higher activity than NiO prepared by ammonia-water precipitation method in catalytic hydrogenolysis (CH) reaction of enzymatic hydrolysis lignin (EHL). The yield of lignin oil reached 85.68 % at 270 °C for 30 min. The catalytic performance was further improved by the introduction of CuO. Under the optimized conditions (290 °C, 120 min), the yield of lignin oil was up to 95.13 % using N-C (4:1) as the catalyst. The GC-MS analysis showed that the lignin oil mainly consisted of phenols, esters, hydrocarbons, and other oxygenated compounds, among which, the phenolic content was up to 57.90 %. These results indicate that the prepared catalyst can effectively break the C-O and C-C bonds in lignin and significantly promote the formation of phenolics.
{"title":"Catalytic hydrogenolysis of lignin with NiO-CuO catalyst via alcohol-water coprecipitation","authors":"Fengkai Liang, Yanbo Yin, Tiantian Jiao, Xiangping Li, Haifeng Zhou, Peng Liang","doi":"10.1016/j.apcata.2024.120082","DOIUrl":"10.1016/j.apcata.2024.120082","url":null,"abstract":"<div><div>Using lignin to produce valuable chemicals can help reduce reliance on fossil fuels. The NiO catalyst prepared by alcohol/water co-precipitation method showed higher activity than NiO prepared by ammonia-water precipitation method in catalytic hydrogenolysis (CH) reaction of enzymatic hydrolysis lignin (EHL). The yield of lignin oil reached 85.68 % at 270 °C for 30 min. The catalytic performance was further improved by the introduction of CuO. Under the optimized conditions (290 °C, 120 min), the yield of lignin oil was up to 95.13 % using N-C (4:1) as the catalyst. The GC-MS analysis showed that the lignin oil mainly consisted of phenols, esters, hydrocarbons, and other oxygenated compounds, among which, the phenolic content was up to 57.90 %. These results indicate that the prepared catalyst can effectively break the C-O and C-C bonds in lignin and significantly promote the formation of phenolics.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"691 ","pages":"Article 120082"},"PeriodicalIF":4.7,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143135266","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 : 2025-02-05DOI: 10.1016/j.apcata.2024.120086
Zhecheng Fang , Sifan Wang , Haoan Fan , Xuezhi Zhao , Huiping Ji , Bolong Li , Zhenyu Zhang , Jianghao Wang , Kaige Wang , Weiyu Song , Reinout Meijboom , Jie Fu
Sorbitol production involves glucose hydrogenation, which requires co-adsorption of glucose and hydrogen on the catalyst surface for high catalytic performance. Binary alloy catalysts can modulate substrate adsorption to achieve better catalytic performance than Raney Ni. Herein, we established a pioneering DFT/ML approach to investigate the adsorption energies of glucose (ΔEGCHO) and H atoms (ΔEH) on 1155 binary alloy catalysts. The Light Gradient Boosting Machine (LGBM) algorithm proved the most effective ML model, predicting ΔEGCHO and ΔEH with R² values of 0.785 and 0.636, respectively. Microkinetic simulation demonstrated a correlation between catalytic activity and adsorption energy, revealing high-performance catalyst screening criteria as ΔEGCHO = −1.45 to −0.65 eV and ΔEH = −0.55–0.00 eV. Nine possible binary alloy catalysts with high predicted activity were identified, with Pd3Mg performing best. The present study highlights the potential of the DFT/ML-assisted approach in the development of efficient glucose hydrogenation binary alloy catalysts.
{"title":"Machine-learning-assisted catalytic performance predictions of binary alloy catalysts for glucose hydrogenation","authors":"Zhecheng Fang , Sifan Wang , Haoan Fan , Xuezhi Zhao , Huiping Ji , Bolong Li , Zhenyu Zhang , Jianghao Wang , Kaige Wang , Weiyu Song , Reinout Meijboom , Jie Fu","doi":"10.1016/j.apcata.2024.120086","DOIUrl":"10.1016/j.apcata.2024.120086","url":null,"abstract":"<div><div>Sorbitol production involves glucose hydrogenation, which requires co-adsorption of glucose and hydrogen on the catalyst surface for high catalytic performance. Binary alloy catalysts can modulate substrate adsorption to achieve better catalytic performance than Raney Ni. Herein, we established a pioneering DFT/ML approach to investigate the adsorption energies of glucose (ΔE<sub>GCHO</sub>) and H atoms (ΔE<sub>H</sub>) on 1155 binary alloy catalysts. The Light Gradient Boosting Machine (LGBM) algorithm proved the most effective ML model, predicting ΔE<sub>GCHO</sub> and ΔE<sub>H</sub> with R² values of 0.785 and 0.636, respectively. Microkinetic simulation demonstrated a correlation between catalytic activity and adsorption energy, revealing high-performance catalyst screening criteria as ΔE<sub>GCHO</sub> = −1.45 to −0.65 eV and ΔE<sub>H</sub> = −0.55–0.00 eV. Nine possible binary alloy catalysts with high predicted activity were identified, with Pd<sub>3</sub>Mg performing best. The present study highlights the potential of the DFT/ML-assisted approach in the development of efficient glucose hydrogenation binary alloy catalysts.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"691 ","pages":"Article 120086"},"PeriodicalIF":4.7,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143135075","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}
The selective hydrogenation of α, β-unsaturated aldehydes/ketones, while preserving other functional groups within the molecule, is of paramount importance in synthetic chemistry for the precise modulation of product structures and properties. This is particularly crucial in the synthesis of complex and high-value organic molecules. As sustainability concerns intensify, the development of catalytic technologies that adhere to green chemistry principles has become an urgent imperative. These advancements not only address the rising demand for chemicals but also respond to the global call to mitigate unsustainable practices. This review focuses on the selective hydrogenation of α, β-unsaturated aldehydes/ketones, highlighting significant progress and breakthroughs in photocatalysis and electrocatalysis within the non-traditional thermal catalysis framework over the past decade. It provides an in-depth analysis of the characteristics and design principles of catalysts, catalytic systems, performance metrics, and the mechanistic pathways involved. Moreover, this review examines the factors influencing the selective hydrogenation of CC/CO bonds, pinpointing potential focal points for the development of green and sustainable hydrogenation systems for these compounds. Through elucidating these advancements, the review aims to offer valuable insights for further innovations in green and sustainable synthetic chemistry.
{"title":"Selective hydrogenation of α, β-unsaturated aldehydes/ketones via photocatalytic and electrocatalytic techniques: A review","authors":"Shunli Shi, Jiaxuan Yang, Ying Li, Yahui Zhu, Weiming Xiao, Shunmin Ding, Shuhua Wang, Chao Chen","doi":"10.1016/j.apcata.2024.120063","DOIUrl":"10.1016/j.apcata.2024.120063","url":null,"abstract":"<div><div>The selective hydrogenation of α, β-unsaturated aldehydes/ketones, while preserving other functional groups within the molecule, is of paramount importance in synthetic chemistry for the precise modulation of product structures and properties. This is particularly crucial in the synthesis of complex and high-value organic molecules. As sustainability concerns intensify, the development of catalytic technologies that adhere to green chemistry principles has become an urgent imperative. These advancements not only address the rising demand for chemicals but also respond to the global call to mitigate unsustainable practices. This review focuses on the selective hydrogenation of α, β-unsaturated aldehydes/ketones, highlighting significant progress and breakthroughs in photocatalysis and electrocatalysis within the non-traditional thermal catalysis framework over the past decade. It provides an in-depth analysis of the characteristics and design principles of catalysts, catalytic systems, performance metrics, and the mechanistic pathways involved. Moreover, this review examines the factors influencing the selective hydrogenation of C<img>C/C<img>O bonds, pinpointing potential focal points for the development of green and sustainable hydrogenation systems for these compounds. Through elucidating these advancements, the review aims to offer valuable insights for further innovations in green and sustainable synthetic chemistry.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"691 ","pages":"Article 120063"},"PeriodicalIF":4.7,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143135090","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 : 2025-02-05DOI: 10.1016/j.apcata.2024.120067
Jie Huang , Bing Yan , Zhansheng Wang , Xu Chen , Zonghui Liu , Bing Xue
Conversion of 2,5-Dimethylfuran (DMF) and Acrylic Acid by Diels–Alder cycloaddition reaction over the Beta zeolites has demonstrated potential for producing renewable para-Xylene (PX). However, the reaction process and the structure-activity correlation were not fully characterized. In this work, Beta zeolites were used to catalyze the Diels–Alder reaction of DMF. The structural characterization, selective poisoning experiments, in-situ FTIR spectra measurements, and kinetic analysis were performed. The results illustrated that the reaction to form PX proceeds by cycloaddition and subsequent decarboxylation over Lewis (L) acid sites, and finally dehydration over Brønsted (B) acid sites. 2,5-dimethylbenzoic acid could not produce PX by decarboxylation over Beta zeolites. The FTIR spectra measurements showed that the B acid sites were incorporated into the reaction network. There were strong diffusion limitations in the H-Beta catalyst during the reaction. When diffusion limitations were eliminated by producing mesopores, the reaction was kinetically limited by the dehydration step.
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