Pub Date : 2025-01-01DOI: 10.1016/S1872-2067(24)60168-3
Fengming Shi , Bin Chen , Jinhai Yu , Ruiqi Zhu , Yu Zheng , Xiaoqiang Huang
ABSTRACT
Vicinal diamines are key motifs widely-found in many pharmaceuticals and biologically active molecules. An appealing approach for synthesizing these molecules is the amination of enamines, but few examples have been explored. With the utilization of nitrogen-centered radicals (NCRs), here we present the development of a dual bio-/photo-catalytic system for achieving enantioselective hydroamination of enamides, which can give easy access to diverse enantioenriched vicinal diamines. These reactions progress efficiently under green light excitation and exhibit excellent enantioselectivities (up to >99% enantiomeric excess). Mechanistic studies uncovered the synergistic effect of the enzyme and the externally added organophotoredox catalyst Rhodamine B (RhB). This work demonstrates the effectiveness of photobiocatalysis to generate and control high-energy radical intermediates, addressing a long-standing challenge in chemical synthesis.
{"title":"Enantioselective biosynthesis of vicinal diamines enabled by synergistic photo/biocatalysis consisting of an ene-reductase and a green-light-excited organic dye","authors":"Fengming Shi , Bin Chen , Jinhai Yu , Ruiqi Zhu , Yu Zheng , Xiaoqiang Huang","doi":"10.1016/S1872-2067(24)60168-3","DOIUrl":"10.1016/S1872-2067(24)60168-3","url":null,"abstract":"<div><h3>ABSTRACT</h3><div>Vicinal diamines are key motifs widely-found in many pharmaceuticals and biologically active molecules. An appealing approach for synthesizing these molecules is the amination of enamines, but few examples have been explored. With the utilization of nitrogen-centered radicals (NCRs), here we present the development of a dual bio-/photo-catalytic system for achieving enantioselective hydroamination of enamides, which can give easy access to diverse enantioenriched vicinal diamines. These reactions progress efficiently under green light excitation and exhibit excellent enantioselectivities (up to >99% enantiomeric excess). Mechanistic studies uncovered the synergistic effect of the enzyme and the externally added organophotoredox catalyst Rhodamine B (RhB). This work demonstrates the effectiveness of photobiocatalysis to generate and control high-energy radical intermediates, addressing a long-standing challenge in chemical synthesis.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"68 ","pages":"Pages 223-229"},"PeriodicalIF":15.7,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143093931","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}
Pub Date : 2025-01-01DOI: 10.1016/S1872-2067(24)60155-5
Caixia Liu , Chaojun Huang , Baiyu Fan , Yan Zhang , Lijing Fang , Yuhe Wang , Qingling Liu , Weichao Wang , Yanguo Chen , Yawei Zhang , Jiancheng Liu , Fang Dong , Ziyin Zhang
ABSTRACT
Understanding the influence of HCl on the NH3-selective catalytic reduction reaction mechanism is crucial for designing highly efficient denitrification catalysts. The formation of chlorate species on the surface of the synthesized SbCeOx catalyst, induced by HCl, significantly enhances low-temperature activity, as evidenced by a 30% increase in NO conversion at 155 °C. Furthermore, it improves N2 selectivity at high temperatures, with a notable 17% increase observed at 405 °C. Both experimental results and density functional theory calculations confirm that chlorate species form at Ce sites. This formation facilitates the creation of oxygen vacancies, boosting the oxygen exchange capacity. It also increases NH3 adsorption at the Ce sites, promotes the formation of Sb-OH, and reduces competitive OH adsorption on these sites. Notably, compared with the reaction mechanism without HCl, the presence of chlorate species enhances NH3 adsorption and activation, which is vital for subsequent catalytic reactions.
{"title":"An unexpected reversal: The smart performance of hydrogen chloride on SbCe catalysts for NH3-SCR reaction","authors":"Caixia Liu , Chaojun Huang , Baiyu Fan , Yan Zhang , Lijing Fang , Yuhe Wang , Qingling Liu , Weichao Wang , Yanguo Chen , Yawei Zhang , Jiancheng Liu , Fang Dong , Ziyin Zhang","doi":"10.1016/S1872-2067(24)60155-5","DOIUrl":"10.1016/S1872-2067(24)60155-5","url":null,"abstract":"<div><h3>ABSTRACT</h3><div>Understanding the influence of HCl on the NH<sub>3</sub>-selective catalytic reduction reaction mechanism is crucial for designing highly efficient denitrification catalysts. The formation of chlorate species on the surface of the synthesized SbCeO<sub><em>x</em></sub> catalyst, induced by HCl, significantly enhances low-temperature activity, as evidenced by a 30% increase in NO conversion at 155 °C. Furthermore, it improves N<sub>2</sub> selectivity at high temperatures, with a notable 17% increase observed at 405 °C. Both experimental results and density functional theory calculations confirm that chlorate species form at Ce sites. This formation facilitates the creation of oxygen vacancies, boosting the oxygen exchange capacity. It also increases NH<sub>3</sub> adsorption at the Ce sites, promotes the formation of Sb-OH, and reduces competitive OH adsorption on these sites. Notably, compared with the reaction mechanism without HCl, the presence of chlorate species enhances NH<sub>3</sub> adsorption and activation, which is vital for subsequent catalytic reactions.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"68 ","pages":"Pages 376-385"},"PeriodicalIF":15.7,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143094369","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}
Pub Date : 2024-12-01DOI: 10.1016/S1872-2067(24)60144-0
Yingying Wei, Yuyao Sun, Yaodong Yu, Yue Shi, Zhe Wu, Lei Wang, Jianping Lai
Electrocatalytic nitrogen reduction reaction under ambient conditions is a promising pathway for ammonia synthesis. Currently nitrogen reduction reactions are carried out in N2-saturated environments and use high-purity nitrogen as feedstock, which is costly. Here, we prepared carbon-coated ultra-low 4d metal Ru-doped liquid metal Ga (Ru0.06/LM@C) for NRR over a wide range of N2 concentrations. Comprehensive analyses show that the introduction of the ultra-low 4d element Ru can effectively adjust the electronic structure through orbital interactions, thus enhancing the adsorption of nitrogen-containing intermediates. The liquid catalyst utilized its mobility to provide a higher density of active sites. In addition, the material Ru0.06/Ga@C itself has the ability to promote product desorption. The three act synergistically to optimize the N2 mass transfer path, thereby increasing the *NNH coverage and further improving the ammonia yield over a wide range of N2 concentrations. The maximum NH3 yield of the catalyst can reach 126.0 μg h−1 mgcat−1 (at –0.3 V vs. RHE) with high purity N2 as feed gas, and the Faraday efficiency is 60.4% at –0.1 V vs. RHE. Over a wide range of N2 concentrations, the NH3 yield of the catalyst was greater than 100 μg h−1 mgcat−1 with a Faraday efficiency higher than 47%. The catalytic performance is much higher than that of solid Ga@C and reported p-block metal-based catalysts.
{"title":"4d Metal-doped liquid Ga for efficient ammonia electrosynthesis at wide N2 concentrations","authors":"Yingying Wei, Yuyao Sun, Yaodong Yu, Yue Shi, Zhe Wu, Lei Wang, Jianping Lai","doi":"10.1016/S1872-2067(24)60144-0","DOIUrl":"10.1016/S1872-2067(24)60144-0","url":null,"abstract":"<div><div>Electrocatalytic nitrogen reduction reaction under ambient conditions is a promising pathway for ammonia synthesis. Currently nitrogen reduction reactions are carried out in N<sub>2</sub>-saturated environments and use high-purity nitrogen as feedstock, which is costly. Here, we prepared carbon-coated ultra-low 4<em>d</em> metal Ru-doped liquid metal Ga (Ru<sub>0.06</sub>/LM@C) for NRR over a wide range of N<sub>2</sub> concentrations. Comprehensive analyses show that the introduction of the ultra-low 4<em>d</em> element Ru can effectively adjust the electronic structure through orbital interactions, thus enhancing the adsorption of nitrogen-containing intermediates. The liquid catalyst utilized its mobility to provide a higher density of active sites. In addition, the material Ru<sub>0.06</sub>/Ga@C itself has the ability to promote product desorption. The three act synergistically to optimize the N<sub>2</sub> mass transfer path, thereby increasing the *NNH coverage and further improving the ammonia yield over a wide range of N<sub>2</sub> concentrations. The maximum NH<sub>3</sub> yield of the catalyst can reach 126.0 μg h<sup>−1</sup> mg<sub>cat</sub><sup>−1</sup> (at –0.3 V <em>vs</em>. RHE) with high purity N<sub>2</sub> as feed gas, and the Faraday efficiency is 60.4% at –0.1 V <em>vs</em>. RHE. Over a wide range of N<sub>2</sub> concentrations, the NH<sub>3</sub> yield of the catalyst was greater than 100 μg h<sup>−1</sup> mg<sub>cat</sub><sup>−1</sup> with a Faraday efficiency higher than 47%. The catalytic performance is much higher than that of solid Ga@C and reported <em>p</em>-block metal-based catalysts.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"67 ","pages":"Pages 194-203"},"PeriodicalIF":15.7,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143170972","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}
Pub Date : 2024-12-01DOI: 10.1016/S1872-2067(24)60139-7
Yi-Fan Xi , Rui-Xing Gao , Ping Fang , Ya-Ping Han , Cong Ma , Tian-Sheng Mei
A novel strategy for site-selective benzylic C–H oxidation has been developed through mediated electrolysis. A bulky maleimide N-oxyl radical (MINO) generated by proton-coupled electrochemical oxidation of N-hydroxymaleimide (NHMI), serves as a hydrogen atom-transfer mediator. Good-to-excellent site selectivity was observed among different substrates, providing a practical approach for site-selective benzylic C–H oxidation. Additionally, the hydrogen-atom transfer mechanism for C–H electrochemical oxidation allows the oxidation to proceed at much lower anode potentials relative to direct electrolysis and with minimal reliance on the substrate's electronic properties.
{"title":"Site-selective benzylic C–H oxidation through mediated electrolysis","authors":"Yi-Fan Xi , Rui-Xing Gao , Ping Fang , Ya-Ping Han , Cong Ma , Tian-Sheng Mei","doi":"10.1016/S1872-2067(24)60139-7","DOIUrl":"10.1016/S1872-2067(24)60139-7","url":null,"abstract":"<div><div>A novel strategy for site-selective benzylic C–H oxidation has been developed through mediated electrolysis. A bulky maleimide <em>N</em>-oxyl radical (MINO) generated by proton-coupled electrochemical oxidation of <em>N</em>-hydroxymaleimide (NHMI), serves as a hydrogen atom-transfer mediator. Good-to-excellent site selectivity was observed among different substrates, providing a practical approach for site-selective benzylic C–H oxidation. Additionally, the hydrogen-atom transfer mechanism for C–H electrochemical oxidation allows the oxidation to proceed at much lower anode potentials relative to direct electrolysis and with minimal reliance on the substrate's electronic properties.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"67 ","pages":"Pages 54-60"},"PeriodicalIF":15.7,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143172203","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}
Pub Date : 2024-12-01DOI: 10.1016/S1872-2067(24)60135-X
Haodi Wang , Feng Jiao , Jingyao Feng , Yuting Sun , Guangjin Hou , Xiulian Pan , Xinhe Bao
The location of aluminum within the framework or extra-framework of zeolites is a critical factor in determining its catalytic performance. Despite extensive research on the identification and formation mechanism of extra-framework aluminum (EFAl), its impact on catalytic performance requires further investigation. Herein, mordenite (MOR) zeolites with comparable acid density within the 8MR and 12MR channels but different EFAl contents were prepared, and their catalytic roles were examined in syngas conversion. Intelligent gravimetric analysis, model experiment of ethylene conversion and thermogravimetric analysis demonstrate that the existence of EFAl species can inhibit the secondary conversion of ethylene to long chain hydrocarbons (i.e., C5+) as well as the over-accumulation of carbonaceous species. However, excessive EFAl species lead to rapid deactivation due to restricted space and thus severe diffusion limitation. MOR zeolite with a moderate amount of EFAl species achieves a superior ethylene selectivity and exhibits an enhanced stability in syngas conversion when combined with ZnAlOx oxide. The insights gained in this work provide important guidance for the design of more efficient zeolite-based catalysts.
{"title":"Role of extra-framework aluminum species within MOR zeolites for syngas conversion via OXZEO catalysis","authors":"Haodi Wang , Feng Jiao , Jingyao Feng , Yuting Sun , Guangjin Hou , Xiulian Pan , Xinhe Bao","doi":"10.1016/S1872-2067(24)60135-X","DOIUrl":"10.1016/S1872-2067(24)60135-X","url":null,"abstract":"<div><div>The location of aluminum within the framework or extra-framework of zeolites is a critical factor in determining its catalytic performance. Despite extensive research on the identification and formation mechanism of extra-framework aluminum (EFAl), its impact on catalytic performance requires further investigation. Herein, mordenite (MOR) zeolites with comparable acid density within the 8MR and 12MR channels but different EFAl contents were prepared, and their catalytic roles were examined in syngas conversion. Intelligent gravimetric analysis, model experiment of ethylene conversion and thermogravimetric analysis demonstrate that the existence of EFAl species can inhibit the secondary conversion of ethylene to long chain hydrocarbons (i.e., C<sub>5+</sub>) as well as the over-accumulation of carbonaceous species. However, excessive EFAl species lead to rapid deactivation due to restricted space and thus severe diffusion limitation. MOR zeolite with a moderate amount of EFAl species achieves a superior ethylene selectivity and exhibits an enhanced stability in syngas conversion when combined with ZnAlO<sub><em>x</em></sub> oxide. The insights gained in this work provide important guidance for the design of more efficient zeolite-based catalysts.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"67 ","pages":"Pages 135-143"},"PeriodicalIF":15.7,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143170975","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}
Pub Date : 2024-12-01DOI: 10.1016/S1872-2067(24)60138-5
Yanling Yang , Peijie Han , Yuanbao Zhang , Jingdong Lin , Shaolong Wan , Yong Wang , Haichao Liu , Shuai Wang
Selective hydrodeoxygenation of lignin derivatives into aromatic compounds is a promising route for the upgrading of lignin feedstocks. Metal carbide catalysts have exhibited excellent selectivity in hydrodeoxygenation reactions, while their structure-activity relationship is still in ambiguity. Herein, a liquid-phase atomic layer deposition method was employed to synthesize W2C/SiO2 catalysts with uniform and size-controllable W2C nanoparticles. For gas-phase hydrodeoxygenation of lignin-derived m-cresol at 350 °C, these W2C/SiO2 catalysts showed superior toluene selectivities (>95%) regardless of the W2C particle size. An optimal W2C particle size of ~7 nm was obtained for achieving the highest W2C-based hydrodeoxygenation rate. In contrast, the turnover rate per surface W site increased almost monotonously as the W2C particle size increased within 0.7‒15 nm, attributable to high-index planes appeared on the larger W2C nanoparticles. Kinetic effects of m-cresol and H2, taken together with temperature-programmed desorption of probe molecules and theoretical treatments, further indicate that the W2C surface is nearly saturated by adsorbed m-cresol or its derivates under the reaction condition and the H-addition of the C7H7* intermediate to form toluene, instead of the initial C-O cleavage in m-cresol, acts as the rate-determining step. A side-by-side comparison between W2C(102) and W2C(001) catalyst surfaces in theoretical simulations of m-cresol hydrodeoxygenation verifies that high-index planes can stabilize kinetically-relevant transition states more effectively than the low-index ones, as a result of more available less-coordinated active sites on the former. The above findings bring new mechanistic insights into the site requirements of supported W2C nanocatalysts, distinct from those metal-catalyzed hydrodeoxygenation of oxygenates.
{"title":"Site requirements of supported W2C nanocatalysts for efficient hydrodeoxygenation of m-cresol to aromatics","authors":"Yanling Yang , Peijie Han , Yuanbao Zhang , Jingdong Lin , Shaolong Wan , Yong Wang , Haichao Liu , Shuai Wang","doi":"10.1016/S1872-2067(24)60138-5","DOIUrl":"10.1016/S1872-2067(24)60138-5","url":null,"abstract":"<div><div>Selective hydrodeoxygenation of lignin derivatives into aromatic compounds is a promising route for the upgrading of lignin feedstocks. Metal carbide catalysts have exhibited excellent selectivity in hydrodeoxygenation reactions, while their structure-activity relationship is still in ambiguity. Herein, a liquid-phase atomic layer deposition method was employed to synthesize W<sub>2</sub>C/SiO<sub>2</sub> catalysts with uniform and size-controllable W<sub>2</sub>C nanoparticles. For gas-phase hydrodeoxygenation of lignin-derived <em>m</em>-cresol at 350 °C, these W<sub>2</sub>C/SiO<sub>2</sub> catalysts showed superior toluene selectivities (>95%) regardless of the W<sub>2</sub>C particle size. An optimal W<sub>2</sub>C particle size of ~7 nm was obtained for achieving the highest W<sub>2</sub>C-based hydrodeoxygenation rate. In contrast, the turnover rate per surface W site increased almost monotonously as the W<sub>2</sub>C particle size increased within 0.7‒15 nm, attributable to high-index planes appeared on the larger W<sub>2</sub>C nanoparticles. Kinetic effects of <em>m</em>-cresol and H<sub>2</sub>, taken together with temperature-programmed desorption of probe molecules and theoretical treatments, further indicate that the W<sub>2</sub>C surface is nearly saturated by adsorbed <em>m</em>-cresol or its derivates under the reaction condition and the H-addition of the C<sub>7</sub>H<sub>7</sub>* intermediate to form toluene, instead of the initial C-O cleavage in <em>m</em>-cresol, acts as the rate-determining step. A side-by-side comparison between W<sub>2</sub>C(102) and W<sub>2</sub>C(001) catalyst surfaces in theoretical simulations of <em>m</em>-cresol hydrodeoxygenation verifies that high-index planes can stabilize kinetically-relevant transition states more effectively than the low-index ones, as a result of more available less-coordinated active sites on the former. The above findings bring new mechanistic insights into the site requirements of supported W<sub>2</sub>C nanocatalysts, distinct from those metal-catalyzed hydrodeoxygenation of oxygenates.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"67 ","pages":"Pages 91-101"},"PeriodicalIF":15.7,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143170976","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}
Pub Date : 2024-12-01DOI: 10.1016/S1872-2067(24)60169-5
Hao Zhang, Yong Wang
{"title":"Efficient low-temp direct air capture methods","authors":"Hao Zhang, Yong Wang","doi":"10.1016/S1872-2067(24)60169-5","DOIUrl":"10.1016/S1872-2067(24)60169-5","url":null,"abstract":"","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"67 ","pages":"Pages 1-3"},"PeriodicalIF":15.7,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143172208","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}
Pub Date : 2024-12-01DOI: 10.1016/S1872-2067(24)60146-4
Guang-Hui Lu, Jian Yu, Ning Li
Both biomass valorization and waste upcycling are important routes to sustain the circular bioeconomy. In this work, we present a chemoenzymatic cascade for selective synthesis of chiral N-arylated aspartic acids from biomass-derived furfural and waste nitrophenols (NPs) by merging robust photo- and electrocatalysis with stereoselective biocatalysis. Concurrent photoelectrocatalytic oxidation of furfural into maleic acid (MA) and fumaric acid (FA) was significantly enhanced by combining catalyst and reaction engineering strategies including identification of a powerful photocatalyst meso-tetra(4-carboxyphenyl)porphyrin, continuous flow technique, enhancing dissolved O2 and paired electrosynthesis. The overall space-time yield (STY) approached 2.8 g L−1 h−1 in a fed-batch process, with the product titer of 28.3 g L−1. Besides, photoelectrosynthesis of MA/FA was effectively fueled by sunlight, with the STY of up to 3.6 g L−1 h−1. Both MA selectivity and yield could be facilely improved to around 89% by reducing the buffer concentrations. Paired electrosynthesis strategy not only resulted in greatly improved MA production at the anode, but also enabled NPs upcycling into value-added aminophenols (APs) at the cathode. The products formed in the two electrode chambers were converted into N-arylated (S)-aspartic acids by a bienzymatic cascade. This work presents a multicatalytic approach for integrating selective biomass valorization and waste upcycling towards sustainable manufacture.
{"title":"A chemoenzymatic cascade for sustainable production of chiral N-arylated aspartic acids from furfural and waste","authors":"Guang-Hui Lu, Jian Yu, Ning Li","doi":"10.1016/S1872-2067(24)60146-4","DOIUrl":"10.1016/S1872-2067(24)60146-4","url":null,"abstract":"<div><div>Both biomass valorization and waste upcycling are important routes to sustain the circular bioeconomy. In this work, we present a chemoenzymatic cascade for selective synthesis of chiral <em>N</em>-arylated aspartic acids from biomass-derived furfural and waste nitrophenols (NPs) by merging robust photo- and electrocatalysis with stereoselective biocatalysis. Concurrent photoelectrocatalytic oxidation of furfural into maleic acid (MA) and fumaric acid (FA) was significantly enhanced by combining catalyst and reaction engineering strategies including identification of a powerful photocatalyst meso-tetra(4-carboxyphenyl)porphyrin, continuous flow technique, enhancing dissolved O<sub>2</sub> and paired electrosynthesis. The overall space-time yield (STY) approached 2.8 g L<sup>−1</sup> h<sup>−1</sup> in a fed-batch process, with the product titer of 28.3 g L<sup>−1</sup>. Besides, photoelectrosynthesis of MA/FA was effectively fueled by sunlight, with the STY of up to 3.6 g L<sup>−1</sup> h<sup>−1</sup>. Both MA selectivity and yield could be facilely improved to around 89% by reducing the buffer concentrations. Paired electrosynthesis strategy not only resulted in greatly improved MA production at the anode, but also enabled NPs upcycling into value-added aminophenols (APs) at the cathode. The products formed in the two electrode chambers were converted into <em>N</em>-arylated (<em>S</em>)-aspartic acids by a bienzymatic cascade. This work presents a multicatalytic approach for integrating selective biomass valorization and waste upcycling towards sustainable manufacture.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"67 ","pages":"Pages 102-111"},"PeriodicalIF":15.7,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143100114","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}
Pub Date : 2024-12-01DOI: 10.1016/S1872-2067(24)60160-9
Tianming Zai , Wei Chen , Jiamin Yuan , Ye Ma , Qinming Wu , Xianfeng Yi , Zhiqiang Liu , Xiangju Meng , Weiliao Liu , Na Sheng , Han Wang , Anmin Zheng , Feng-Shou Xiao
Design and preparation of highly efficient zeolite catalysts for gas-phase Beckmann rearrangement of cyclohexanone oxime to caprolactam are attractive but still challenging. Herein, we show a one-pot synthesis of silicalite-1 zeolite nanosheets with rich H-bonded silanols. The key to this success is the use of urea in the synthetic system. Catalytic tests of cyclohexanone oxime gas-phase Beckmann rearrangement show that the silicalite-1 zeolite nanosheets with H-bonded silanols exhibit higher selectivity for caprolactam and longer reaction lifetime than those of the conventional silicalite-1 zeolite. Theoretical simulations reveal that the ammonium decomposed by urea is a critical additive for the formation of H-bond silanols. Obviously, one-pot synthesis of silicalite-1 zeolite nanosheets with rich H-bonded silanols plus excellent catalytic performance in the Beckmann rearrangement offer a new opportunity for development of highly efficient zeolites for catalytic applications in the future.
{"title":"Silicalite-1 zeolite nanosheets with rich H-bonded silanols for boosting vapor-phase Beckmann rearrangement: One-pot synthesis and theoretical investigation","authors":"Tianming Zai , Wei Chen , Jiamin Yuan , Ye Ma , Qinming Wu , Xianfeng Yi , Zhiqiang Liu , Xiangju Meng , Weiliao Liu , Na Sheng , Han Wang , Anmin Zheng , Feng-Shou Xiao","doi":"10.1016/S1872-2067(24)60160-9","DOIUrl":"10.1016/S1872-2067(24)60160-9","url":null,"abstract":"<div><div>Design and preparation of highly efficient zeolite catalysts for gas-phase Beckmann rearrangement of cyclohexanone oxime to caprolactam are attractive but still challenging. Herein, we show a one-pot synthesis of silicalite-1 zeolite nanosheets with rich H-bonded silanols. The key to this success is the use of urea in the synthetic system. Catalytic tests of cyclohexanone oxime gas-phase Beckmann rearrangement show that the silicalite-1 zeolite nanosheets with H-bonded silanols exhibit higher selectivity for caprolactam and longer reaction lifetime than those of the conventional silicalite-1 zeolite. Theoretical simulations reveal that the ammonium decomposed by urea is a critical additive for the formation of H-bond silanols. Obviously, one-pot synthesis of silicalite-1 zeolite nanosheets with rich H-bonded silanols plus excellent catalytic performance in the Beckmann rearrangement offer a new opportunity for development of highly efficient zeolites for catalytic applications in the future.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"67 ","pages":"Pages 82-90"},"PeriodicalIF":15.7,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143172202","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}
Pub Date : 2024-12-01DOI: 10.1016/S1872-2067(24)60136-1
Hantao Gong , Caihao Deng , Peipei He , Mingjie Liu , Yiliang Cai , Yiwen Yang , Qiwei Yang , Zongbi Bao , Qilong Ren , Siyu Yao , Zhiguo Zhang
Selective photocatalytic aerobic oxidation of methane to value-added chemicals offers a promising pathway for sustainable chemical industry, yet remains a huge challenge owing to the consecutive overoxidation of primary products. Here, a type II heterojunction were constructed in Ag-AgBr/ZnO to reduce the oxidation potential of stimulated holes and prevent the undesirable CH4 overoxidation side reactions. For photocatalytic oxidation of methane under ambient temperature, the products yield of 1499.6 μmol gcat−1 h−1 with a primary products selectivity of 77.9% was achieved over Ag-AgBr/ZnO, which demonstrate remarkable improvement compared to Ag/ZnO (1089.9 μmol gcat−1 h−1, 40.1%). The superior activity and selectivity result from the promoted charge separation and the redox potential matching with methane activation after introducing AgBr species. Mechanism investigation elucidated that the photo-generated holes transferred from the valence band of ZnO to that of AgBr, which prevent H2O oxidation and enhance the selective generation of •OOH radical.
{"title":"Selective photooxidation of methane to C1 oxygenates by constructing heterojunction photocatalyst with mild oxidation ability","authors":"Hantao Gong , Caihao Deng , Peipei He , Mingjie Liu , Yiliang Cai , Yiwen Yang , Qiwei Yang , Zongbi Bao , Qilong Ren , Siyu Yao , Zhiguo Zhang","doi":"10.1016/S1872-2067(24)60136-1","DOIUrl":"10.1016/S1872-2067(24)60136-1","url":null,"abstract":"<div><div>Selective photocatalytic aerobic oxidation of methane to value-added chemicals offers a promising pathway for sustainable chemical industry, yet remains a huge challenge owing to the consecutive overoxidation of primary products. Here, a type II heterojunction were constructed in Ag-AgBr/ZnO to reduce the oxidation potential of stimulated holes and prevent the undesirable CH<sub>4</sub> overoxidation side reactions. For photocatalytic oxidation of methane under ambient temperature, the products yield of 1499.6 μmol g<sub>cat</sub><sup>−1</sup> h<sup>−1</sup> with a primary products selectivity of 77.9% was achieved over Ag-AgBr/ZnO, which demonstrate remarkable improvement compared to Ag/ZnO (1089.9 μmol g<sub>cat</sub><sup>−1</sup> h<sup>−1</sup>, 40.1%). The superior activity and selectivity result from the promoted charge separation and the redox potential matching with methane activation after introducing AgBr species. Mechanism investigation elucidated that the photo-generated holes transferred from the valence band of ZnO to that of AgBr, which prevent H<sub>2</sub>O oxidation and enhance the selective generation of •OOH radical.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"67 ","pages":"Pages 61-70"},"PeriodicalIF":15.7,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143172204","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}
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