Pub Date : 2025-03-06DOI: 10.1016/j.mcat.2025.114992
Li Li , Zhiyao Huang , Yifan Yang , Yaoyao Wei , Guokui Liu , Qiying Xia , Honglei Wang
The electrocatalytic reduction of carbon monoxide (CO) to high-value multicarbon chemicals represents an effective strategy for achieving a sustainable carbon cycle. In recent years, researchers have developed a variety of highly efficient catalysts for the reduction of CO. Among these materials, non-metallic catalysts demonstrate considerable energy application due to their environmentally friendly, low-cost and compositionally tunable properties. In this study, we innovatively designed a non-metallic catalyst (B/g-C3N4/GN) by introducing boron (B) atoms to the heterostructure of graphitic carbon nitride (g-C3N4) and graphene (GN) to reduce CO through first-principle calculations. The catalyst effectively promotes the conversion of CO to ethylene (CH2CH2) with a free energy increase of 0.22 eV for the potential-determining step (PDS), and the energy barrier for C–C coupling is only 0.37 eV, which demonstrates the efficient and stable catalytic performance. The design of the B/g-C3N4/GN material provides a new approach in the field of electrocatalysis.
{"title":"Potentials and reaction mechanisms of metal-free B/g-C3N4/graphene catalyst for reducing carbon monoxide to ethylene","authors":"Li Li , Zhiyao Huang , Yifan Yang , Yaoyao Wei , Guokui Liu , Qiying Xia , Honglei Wang","doi":"10.1016/j.mcat.2025.114992","DOIUrl":"10.1016/j.mcat.2025.114992","url":null,"abstract":"<div><div>The electrocatalytic reduction of carbon monoxide (CO) to high-value multicarbon chemicals represents an effective strategy for achieving a sustainable carbon cycle. In recent years, researchers have developed a variety of highly efficient catalysts for the reduction of CO. Among these materials, non-metallic catalysts demonstrate considerable energy application due to their environmentally friendly, low-cost and compositionally tunable properties. In this study, we innovatively designed a non-metallic catalyst (B/g-C<sub>3</sub>N<sub>4</sub>/GN) by introducing boron (B) atoms to the heterostructure of graphitic carbon nitride (g-C<sub>3</sub>N<sub>4</sub>) and graphene (GN) to reduce CO through first-principle calculations. The catalyst effectively promotes the conversion of CO to ethylene (CH<sub>2</sub>CH<sub>2</sub>) with a free energy increase of 0.22 eV for the potential-determining step (PDS), and the energy barrier for C–C coupling is only 0.37 eV, which demonstrates the efficient and stable catalytic performance. The design of the B/g-C<sub>3</sub>N<sub>4</sub>/GN material provides a new approach in the field of electrocatalysis.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"578 ","pages":"Article 114992"},"PeriodicalIF":3.9,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143552812","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 : 2025-03-06DOI: 10.1016/j.mcat.2025.114978
Binxin Lv , Jiayue Yu , Fengchen Zhou , Zizi Wang , Junjun Zhang , Yifan Zhang , Yang Wu , Yong Wang , Wen Luo
Urea electrosynthesis plays a vital role in the nitrogen cycle, promoting carbon neutrality while also being energy-efficient. However, the complexities involved in the simultaneous of carbon and nitrogen-containing species significantly hinder the selectivity and yield of urea. In this study, we report a CuZn bimetallic catalyst that is capable of converting CO2 and NO3⁻ into urea, with a maximum Faraday efficiency of 40% at -0.6 V vs. RHE, alongside an impressive urea yield rate of 304.8 mmol h⁻¹ gcat⁻¹ at -0.9 V vs. RHE, surpassing the performance of both monometallic Cu and Zn catalysts. In situ spectroscopic analysis demonstrates that the Cu sites within CuZn facilitates the adsorption and activation of CO2 and NO3⁻, while Zn sites additionally facilitate CO2 adsorption and reduces the adsorption strength of *CO and *NH2 on the catalyst surface, collectively promoting the formation of *CONH2 as a key intermediate in urea synthesis. This study highlights the unique role of zinc in urea synthesis, offers new insights into optimizing the performance of copper-zinc catalysts, and serves as a valuable reference for future research on the role of zinc in urea synthesis.
{"title":"Unraveling the enhanced urea selectivity in electroreduction of CO2 and nitrate over Bimetallic CuZn catalysts","authors":"Binxin Lv , Jiayue Yu , Fengchen Zhou , Zizi Wang , Junjun Zhang , Yifan Zhang , Yang Wu , Yong Wang , Wen Luo","doi":"10.1016/j.mcat.2025.114978","DOIUrl":"10.1016/j.mcat.2025.114978","url":null,"abstract":"<div><div>Urea electrosynthesis plays a vital role in the nitrogen cycle, promoting carbon neutrality while also being energy-efficient. However, the complexities involved in the simultaneous of carbon and nitrogen-containing species significantly hinder the selectivity and yield of urea. In this study, we report a CuZn bimetallic catalyst that is capable of converting CO<sub>2</sub> and NO<sub>3</sub><sup>⁻</sup> into urea, with a maximum Faraday efficiency of 40% at -0.6 V vs. RHE, alongside an impressive urea yield rate of 304.8 mmol h<sup>⁻¹</sup> g<sub>cat</sub><sup>⁻¹</sup> at -0.9 V vs. RHE, surpassing the performance of both monometallic Cu and Zn catalysts. In situ spectroscopic analysis demonstrates that the Cu sites within CuZn facilitates the adsorption and activation of CO<sub>2</sub> and NO<sub>3</sub><sup>⁻</sup>, while Zn sites additionally facilitate CO<sub>2</sub> adsorption and reduces the adsorption strength of *CO and *NH<sub>2</sub> on the catalyst surface, collectively promoting the formation of *CONH<sub>2</sub> as a key intermediate in urea synthesis. This study highlights the unique role of zinc in urea synthesis, offers new insights into optimizing the performance of copper-zinc catalysts, and serves as a valuable reference for future research on the role of zinc in urea synthesis.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"578 ","pages":"Article 114978"},"PeriodicalIF":3.9,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143562816","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}
Halide perovskites, as emerging semiconductor materials, exhibit great potential in photocatalytic hydrogen evolution. However, perovskite powders prepared through the conventional co-precipitation method typically form large-sized particles with diameters of several tens of micrometers, resulting in low specific surface area and limited active sites, which seriously compromise their catalytic efficiency. Herein, a spatially confined growth method is developed to grow small-sized mixed halide perovskite FAPbBr3-xIx (FA = CH(NH2)2+) nanocrystals within MCM-41 molecular sieve for photocatalytic hydroiodic acid splitting. This developed method significantly increases the specific surface area, provides more reaction sites, and promotes the separation of carriers for the perovskite nanocrystal. When loading with Pt as the cocatalyst, 40 % MCM-41@FAPbBr3-xIx composite demonstrates excellent photocatalytic H2 evolution activity of 2260 μmol h−1. This work presents an inspiring advancement in confined growth tactics for perovskite nanocrystals to achieve efficient photocatalytic hydrogen evolution.
{"title":"Space-confined growth of halide perovskite nanocrystals for enhanced photocatalytic hydrogen evolution","authors":"Xue Li, Miaomiao Gao, Yaqiang Wu, Hui Fu, Qianqian Zhang, Jinghang Chen, Zeyan Wang, Zhaoke Zheng, Hefeng Cheng, Yuanyuan Liu, Baibiao Huang, Peng Wang","doi":"10.1016/j.mcat.2025.114981","DOIUrl":"10.1016/j.mcat.2025.114981","url":null,"abstract":"<div><div>Halide perovskites, as emerging semiconductor materials, exhibit great potential in photocatalytic hydrogen evolution. However, perovskite powders prepared through the conventional co-precipitation method typically form large-sized particles with diameters of several tens of micrometers, resulting in low specific surface area and limited active sites, which seriously compromise their catalytic efficiency. Herein, a spatially confined growth method is developed to grow small-sized mixed halide perovskite FAPbBr<sub>3-x</sub>I<sub>x</sub> (FA = CH(NH<sub>2</sub>)<sub>2</sub><sup>+</sup>) nanocrystals within MCM-41 molecular sieve for photocatalytic hydroiodic acid splitting. This developed method significantly increases the specific surface area, provides more reaction sites, and promotes the separation of carriers for the perovskite nanocrystal. When loading with Pt as the cocatalyst, 40 % MCM-41@FAPbBr<sub>3-x</sub>I<sub>x</sub> composite demonstrates excellent photocatalytic H<sub>2</sub> evolution activity of 2260 μmol h<sup>−1</sup>. This work presents an inspiring advancement in confined growth tactics for perovskite nanocrystals to achieve efficient photocatalytic hydrogen evolution.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"578 ","pages":"Article 114981"},"PeriodicalIF":3.9,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143562817","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 : 2025-03-06DOI: 10.1016/j.mcat.2025.114994
Yarao Gao , Hongyao Zhao , Mengting Liu , Yanyun Wang , Yangping Zhang , Linzhi Zhai , Xiang Liu , Feng Zeng , Jianming Pan , Danhong Shang , Fu Yang
Photothermal hybrids composed of nanocarbon and metal species are promising in solar-driven photothermal conversion and later application of water purification. Herein, the photothermal hybrid with surface-polarized carbon nanotube (CNT) twined oxygen vacancy-engineered cuprous oxides was constructed. The surface polar oxygen and nitrogen moieties were introduced onto the CNT, enriching the surface polarity of the nanocarbon, which further twined the in-situ generated oxygen vacancy-engineered cuprous oxides. The constructed catalyst was endowed with abundant Cu(I) reactive sites and oxygen vacancy, providing the efficient trapping effect and enough exposed active sites to trigger improved peroxymonosulfate (PMS) activation. In addition, the obtained catalyst affords superior photothermal conversion efficiency, thereby showcasing the great potential in solar-driven water purification. Therefore, the catalyst shows excellent bisphenol A (BPA) degradation performance with a reaction rate constant of 0.47 min-1, and activation energy (Ea=9.38 kJ·mol-1).. The reaction mechanism study indicates the main contribution of singlet oxygen and superoxide radicals in the BPA degradation. More importantly, the obtained catalyst affords the excellent total organic carbon (TOC) removal ability for mixed contaminants, higher than that of single contaminant removal, which shows great potential for practical complicated wastewater purification. Finally, the obtained photothermal hybrids were anchored onto the tailored sponge through a hydrogel tethering strategy, which acts as a monolith evaporator to enable cleanwater regeneration and contaminant degradation.
{"title":"Construction of photothermal hybrid with surface-polarized carbon nanotube twined oxygen-vacancy engineered cuprous oxide for improved PMS activation and water purification","authors":"Yarao Gao , Hongyao Zhao , Mengting Liu , Yanyun Wang , Yangping Zhang , Linzhi Zhai , Xiang Liu , Feng Zeng , Jianming Pan , Danhong Shang , Fu Yang","doi":"10.1016/j.mcat.2025.114994","DOIUrl":"10.1016/j.mcat.2025.114994","url":null,"abstract":"<div><div>Photothermal hybrids composed of nanocarbon and metal species are promising in solar-driven photothermal conversion and later application of water purification. Herein, the photothermal hybrid with surface-polarized carbon nanotube (CNT) twined oxygen vacancy-engineered cuprous oxides was constructed. The surface polar oxygen and nitrogen moieties were introduced onto the CNT, enriching the surface polarity of the nanocarbon, which further twined the in-situ generated oxygen vacancy-engineered cuprous oxides. The constructed catalyst was endowed with abundant Cu(I) reactive sites and oxygen vacancy, providing the efficient trapping effect and enough exposed active sites to trigger improved peroxymonosulfate (PMS) activation. In addition, the obtained catalyst affords superior photothermal conversion efficiency, thereby showcasing the great potential in solar-driven water purification. Therefore, the catalyst shows excellent bisphenol A (BPA) degradation performance with a reaction rate constant of 0.47 min<sup>-1</sup>, and activation energy (Ea=9.38 kJ<strong>·</strong>mol<sup>-1</sup>).. The reaction mechanism study indicates the main contribution of singlet oxygen and superoxide radicals in the BPA degradation. More importantly, the obtained catalyst affords the excellent total organic carbon (TOC) removal ability for mixed contaminants, higher than that of single contaminant removal, which shows great potential for practical complicated wastewater purification. Finally, the obtained photothermal hybrids were anchored onto the tailored sponge through a hydrogel tethering strategy, which acts as a monolith evaporator to enable cleanwater regeneration and contaminant degradation.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"578 ","pages":"Article 114994"},"PeriodicalIF":3.9,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143562818","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}
L-malic acid (MA) is an important four-carbon platform compound, with wide applications in food, pharmaceuticals, and cosmetics. Malate dehydrogenase (MDH), which also catalyzes the reduction of oxaloacetate (OAA) as the reaction is reversible, is the key enzyme for microbial production of L-MA. Here, machine-learning-guided protein engineering was applied to AnMDH from Aspergillus niger, resulting in the best variant G212A/G234 V with a remarkable 11-fold improvement of enzyme activity. Then, the efficient L-MA-producing strain A. niger RG020 was constructed by introducing AnMDHG212A/G234V into A. niger RG018. Shake-flask and bioreactor studies showed that A. niger RG020 had an increased L-MA production rate and yield compared to the parental strain RG018. In a 5-L batch bioreactor, the fermentation period was shortened from 146 to 104 h, with the productivity of MA increasing from 0.93 to 1.42 g/L/h. Our work provides practical guidance for improving the productivity of industrial strains.
{"title":"Machine learning-guided malate dehydrogenase engineering for improved production of L-malic acid in Aspergillus niger","authors":"Zihan Zhang , Yuanyuan Zheng , Chi Zhang, Qing Xu, Feng Xue","doi":"10.1016/j.mcat.2025.114990","DOIUrl":"10.1016/j.mcat.2025.114990","url":null,"abstract":"<div><div>L-malic acid (MA) is an important four-carbon platform compound, with wide applications in food, pharmaceuticals, and cosmetics. Malate dehydrogenase (MDH), which also catalyzes the reduction of oxaloacetate (OAA) as the reaction is reversible, is the key enzyme for microbial production of L-MA. Here, machine-learning-guided protein engineering was applied to <em>An</em>MDH from <em>Aspergillus niger</em>, resulting in the best variant G212A/G234 V with a remarkable 11-fold improvement of enzyme activity. Then, the efficient L-MA-producing strain <em>A. niger</em> RG020 was constructed by introducing <em>An</em>MDH<sup>G212A/G234V</sup> into <em>A. niger</em> RG018. Shake-flask and bioreactor studies showed that <em>A. niger</em> RG020 had an increased L-MA production rate and yield compared to the parental strain RG018. In a 5-L batch bioreactor, the fermentation period was shortened from 146 to 104 h, with the productivity of MA increasing from 0.93 to 1.42 g/L/h. Our work provides practical guidance for improving the productivity of industrial strains.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"578 ","pages":"Article 114990"},"PeriodicalIF":3.9,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143563446","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 : 2025-03-05DOI: 10.1016/j.mcat.2025.114931
Chaozheng He , Ye Shen , Long Lin , Kun Xie , Songshan Gao , Yaowei Liu
The activity and selectivity of nitrogen fixation is an urgent problem to be solved in research and design of efficient electrocatalysts. In this work, we systematically researched the feasibility of a single transition metal (TM) atoms supported on graphene-like BC3N2 for electrocatalytic nitrogen (N2) fixation by using the density functional theory (DFT) calculations. The results shown that single TM atoms could embed on BC3N2 monolayer steadily and activate nitrogen molecule efficiently to facilitate NRR process. In addition, the VN-Nb@BC3N2 system exhibited excellent NRR activity due to its extremely low limiting potentials which is 0.46 V. The NRR activity of VN-Nb@BC3N2 system was origin from the weakening effect of antibonding and radical-like effect of d-2π*. The VN-Nb@BC3N2 system was selected not only benefitting from its high NRR activity but also its high selectivity which the HER limiting potentials is 0.56 V. This work may serve as guidance for designing NRR catalysts and understanding the mechanism of N2 fixation.
{"title":"Efficient electrocatalytic N2 fixation over BC3N2 monolayer: A computational screening of single-atom catalysts","authors":"Chaozheng He , Ye Shen , Long Lin , Kun Xie , Songshan Gao , Yaowei Liu","doi":"10.1016/j.mcat.2025.114931","DOIUrl":"10.1016/j.mcat.2025.114931","url":null,"abstract":"<div><div>The activity and selectivity of nitrogen fixation is an urgent problem to be solved in research and design of efficient electrocatalysts. In this work, we systematically researched the feasibility of a single transition metal (TM) atoms supported on graphene-like BC<sub>3</sub>N<sub>2</sub> for electrocatalytic nitrogen (N<sub>2</sub>) fixation by using the density functional theory (DFT) calculations. The results shown that single TM atoms could embed on BC<sub>3</sub>N<sub>2</sub> monolayer steadily and activate nitrogen molecule efficiently to facilitate NRR process. In addition, the V<sub>N</sub>-Nb@BC<sub>3</sub>N<sub>2</sub> system exhibited excellent NRR activity due to its extremely low limiting potentials which is 0.46 V. The NRR activity of V<sub>N</sub>-Nb@BC<sub>3</sub>N<sub>2</sub> system was origin from the weakening effect of antibonding and radical-like effect of <em>d</em>-2<em>π</em>*. The V<sub>N</sub>-Nb@BC<sub>3</sub>N<sub>2</sub> system was selected not only benefitting from its high NRR activity but also its high selectivity which the HER limiting potentials is 0.56 V. This work may serve as guidance for designing NRR catalysts and understanding the mechanism of N<sub>2</sub> fixation.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"577 ","pages":"Article 114931"},"PeriodicalIF":3.9,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143549507","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 : 2025-03-05DOI: 10.1016/j.mcat.2025.114975
Man Jiang , Rong-Zhen Zhang , Hui Liu , Kai-Kai Niu , Ling-Bao Xing
Due to the high bond energy and stability of N = N double bond, their reduction using low-energy visible light remains a great challenge. We herein present the development and application of a novel perylene-3,4,9,10-tetracarboxylic dianhydride-based photocatalyst, which generates anionic radicals in situ upon reduction by vitamin C and demonstrates significant red light catalytic capabilities. The catalyst effectively reduced azo bonds under red light, yielding various substituted azobenzenes with moderate to good efficiency. Additionally, it facilitated the dehalogenation of bromoacetophenone, highlighting its potential in small-molecule pharmaceutical synthesis and pre-drug design. The findings indicate that red light-activated photocatalysis can offer a versatile and efficient approach for complex organic transformations, addressing challenges in bio-optical window applications and expanding the toolkit for synthetic chemistry and biomedicine.
{"title":"Red light initiated azo bond reduction with perylene-3,4,9,10-tetracarboxylic dianhydride radical anions","authors":"Man Jiang , Rong-Zhen Zhang , Hui Liu , Kai-Kai Niu , Ling-Bao Xing","doi":"10.1016/j.mcat.2025.114975","DOIUrl":"10.1016/j.mcat.2025.114975","url":null,"abstract":"<div><div>Due to the high bond energy and stability of N = N double bond, their reduction using low-energy visible light remains a great challenge. We herein present the development and application of a novel perylene-3,4,9,10-tetracarboxylic dianhydride-based photocatalyst, which generates anionic radicals in situ upon reduction by vitamin C and demonstrates significant red light catalytic capabilities. The catalyst effectively reduced azo bonds under red light, yielding various substituted azobenzenes with moderate to good efficiency. Additionally, it facilitated the dehalogenation of bromoacetophenone, highlighting its potential in small-molecule pharmaceutical synthesis and pre-drug design. The findings indicate that red light-activated photocatalysis can offer a versatile and efficient approach for complex organic transformations, addressing challenges in bio-optical window applications and expanding the toolkit for synthetic chemistry and biomedicine.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"577 ","pages":"Article 114975"},"PeriodicalIF":3.9,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143549509","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 : 2025-03-05DOI: 10.1016/j.mcat.2025.114976
Meng Lei , Yuting Xue , Linfeng Gan , Boai Li , Yongchao Lu , Qingru Yang , Wen Wang , Shiwei Wang , Qing Su , Qiaolin Wu
Covalent organic frameworks (COFs) have been considered as a family of attractive photocatalysts, which have shown unique advantages in photocatalytic applications. Multicomponent polycondensation strategy is growing as one of the most important methods for syntheses of functionalized COFs materials. Herein, under solvothermal conditions, four building blocks of 2‑hydroxy-1,3,5-benzenetrialdehyde (HTB), 2,4,6-trihydroxy-1,3,5-benzenetrialdehyde (TTB), benzidine (BD), 3,3′-dimethyl-[1,1′-biphenyl]-4,4′-diamine (DMBZ) were selected to synthesize ketoenamine-linked framework material DBTH4-COF with high crystallinity and stability. The resultant COF has a suitable optical band gap, strong photocurrent response and low impedance, indicative of high potential for heterogeneous photocatalysis. After evaluation, DBTH4-COF exhibited the preminent photocatalytic performance in photosynthesis of benzimidazoles. Cycling experiments also showed high stability and recyclability of the DBTH4-COF. The high-performance DBTH4-COF was further employed as a heterogeneous catalyst for photocatalytic oxidative of amines to imines and oxidation of tetrahydroisoquinoline to dihydroisoquinolone. Some control experiments were performed to gain further insights into the nature of photocatalysis. The current research also provided a valuable approach for developing COFs catalysts to meet challenges in photocatalytic organic transformations.
{"title":"Highly crystalline multi-component covalent organic frameworks for photocatalytic organic conversion","authors":"Meng Lei , Yuting Xue , Linfeng Gan , Boai Li , Yongchao Lu , Qingru Yang , Wen Wang , Shiwei Wang , Qing Su , Qiaolin Wu","doi":"10.1016/j.mcat.2025.114976","DOIUrl":"10.1016/j.mcat.2025.114976","url":null,"abstract":"<div><div>Covalent organic frameworks (COFs) have been considered as a family of attractive photocatalysts, which have shown unique advantages in photocatalytic applications. Multicomponent polycondensation strategy is growing as one of the most important methods for syntheses of functionalized COFs materials. Herein, under solvothermal conditions, four building blocks of 2‑hydroxy-1,3,5-benzenetrialdehyde (HTB), 2,4,6-trihydroxy-1,3,5-benzenetrialdehyde (TTB), benzidine (BD), 3,3′-dimethyl-[1,1′-biphenyl]-4,4′-diamine (DMBZ) were selected to synthesize ketoenamine-linked framework material DBTH4-COF with high crystallinity and stability. The resultant COF has a suitable optical band gap, strong photocurrent response and low impedance, indicative of high potential for heterogeneous photocatalysis. After evaluation, DBTH4-COF exhibited the preminent photocatalytic performance in photosynthesis of benzimidazoles. Cycling experiments also showed high stability and recyclability of the DBTH4-COF. The high-performance DBTH4-COF was further employed as a heterogeneous catalyst for photocatalytic oxidative of amines to imines and oxidation of tetrahydroisoquinoline to dihydroisoquinolone. Some control experiments were performed to gain further insights into the nature of photocatalysis. The current research also provided a valuable approach for developing COFs catalysts to meet challenges in photocatalytic organic transformations.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"577 ","pages":"Article 114976"},"PeriodicalIF":3.9,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143549510","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 : 2025-03-05DOI: 10.1016/j.mcat.2025.114974
Xiaotong Du, Ruixuan Bai, Nan Jiang, Baoling Chen, Liangyu Zheng
Optical diaryl α-hydroxyl amides are important chiral blocks for biologically active compounds. Given the less reactive keto carbonyl groups, diaryl α-keto amides are difficult to reduce; thus, the corresponding α-hydroxyl amides cannot be obtained. Here an “ene”-reductase (YqjM) from Bacillus subtilis was found to possess a promiscuous ability for enantioselective reduction of diaryl α-keto amide (1a) to obtain α-hydroxy amide 1b, but with poor activity and stereoselectivity. Structure-guided, iterative mutagenesis provided a YqjM variant Y28A/Y169I, which could achieve enantioselective conversion efficiently. The product (R)-1b with 84.8 ± 1.3 % yield and 95.6 ± 1.5 % e.e. was achieved within 4 h. With the Y28A/Y169I in hand, other diaryl α-hydroxy amides were also obtained. The non-natural carbonyl reduction mechanism catalyzed by Y28A/Y169I was given by a series of experimental evaluation and molecular dynamics (MD) simulation. This study provides a much simply, rapidly, environmentally friendly, and cost-effectively unconventional route to achieve optical diaryl α-hydroxy amides that are previously difficult to access. The simplified reaction operations not requiring a photocatalyst and blue light, and mild reaction conditions can greatly improve its application potential of the reaction.
{"title":"Engineering a non-naturally enantioselective carbonyl reduction of diaryl α-keto amides by an “ene”-reductase from Bacillus subtilis and its mutant enzymes","authors":"Xiaotong Du, Ruixuan Bai, Nan Jiang, Baoling Chen, Liangyu Zheng","doi":"10.1016/j.mcat.2025.114974","DOIUrl":"10.1016/j.mcat.2025.114974","url":null,"abstract":"<div><div>Optical diaryl α-hydroxyl amides are important chiral blocks for biologically active compounds. Given the less reactive keto carbonyl groups, diaryl α-keto amides are difficult to reduce; thus, the corresponding α-hydroxyl amides cannot be obtained. Here an “ene”-reductase (YqjM) from <em>Bacillus subtilis</em> was found to possess a promiscuous ability for enantioselective reduction of diaryl α-keto amide (<strong>1a</strong>) to obtain α-hydroxy amide <strong>1b</strong>, but with poor activity and stereoselectivity. Structure-guided, iterative mutagenesis provided a YqjM variant Y28A/Y169I, which could achieve enantioselective conversion efficiently. The product (<em>R</em>)-<strong>1b</strong> with 84.8 ± 1.3 % yield and 95.6 ± 1.5 % <em>e.e.</em> was achieved within 4 h. With the Y28A/Y169I in hand, other diaryl α-hydroxy amides were also obtained. The non-natural carbonyl reduction mechanism catalyzed by Y28A/Y169I was given by a series of experimental evaluation and molecular dynamics (MD) simulation. This study provides a much simply, rapidly, environmentally friendly, and cost-effectively unconventional route to achieve optical diaryl α-hydroxy amides that are previously difficult to access. The simplified reaction operations not requiring a photocatalyst and blue light, and mild reaction conditions can greatly improve its application potential of the reaction.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"577 ","pages":"Article 114974"},"PeriodicalIF":3.9,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143549511","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 : 2025-03-05DOI: 10.1016/j.mcat.2025.114956
Bruna Soares dos Reis Aranha , Fabiana Pereira de Sousa , Alem-Mar Bernardes Goncalves , Gilberto Maia , Diego Carvalho Barbosa Alves
Highlighted by the agreement and meetings promoted by the UN in recent years, it is noted the worldwide concern to combat the emission of greenhouse gases in order to slow the warming of the planet. We report the electrochemical reduction of CO2 to oxalic acid with 48.5 % Faradaic efficiency at -1.0 V (vs. NHE) in aprotic medium. The study shows the influence of copper dispersion on reduced graphene oxide surface as a nanostructured catalyst to produce oxalic acid.
{"title":"Copper particles-dispersed on graphene oxide has high faradaic efficiency to produce oxalic acid in aprotic medium.","authors":"Bruna Soares dos Reis Aranha , Fabiana Pereira de Sousa , Alem-Mar Bernardes Goncalves , Gilberto Maia , Diego Carvalho Barbosa Alves","doi":"10.1016/j.mcat.2025.114956","DOIUrl":"10.1016/j.mcat.2025.114956","url":null,"abstract":"<div><div>Highlighted by the agreement and meetings promoted by the UN in recent years, it is noted the worldwide concern to combat the emission of greenhouse gases in order to slow the warming of the planet. We report the electrochemical reduction of CO<sub>2</sub> to oxalic acid with 48.5 % Faradaic efficiency at -1.0 V (vs. NHE) in aprotic medium. The study shows the influence of copper dispersion on reduced graphene oxide surface as a nanostructured catalyst to produce oxalic acid.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"577 ","pages":"Article 114956"},"PeriodicalIF":3.9,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143549508","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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