Pub Date : 2025-01-01DOI: 10.1016/S1872-2067(24)60177-4
Bailing Zhong , Jundie Hu , Xiaogang Yang , Yinying Shu , Yahui Cai , Chang Ming Li , Jiafu Qu
ABSTRACT
Metal-organic frameworks (MOFs) serve as highly effective hosts for ultrasmall metal species, creating advanced nanocatalysts with superior catalytic performance, stability, and selective activity. The synergistic interplay between metal species confined within MOF nanopores and their active sites enhances catalytic efficiency in CO2 hydrogenation reactions. Herein, recent advancements in synthesizing metal-confined MOFs are discussed, along with their applications in catalyzing CO2 conversion through various methods such as photocatalysis, thermal catalysis, and photothermal catalysis. Additionally, we further emphasize the fundamental principles and factors that influence various types of catalytic CO2 hydrogenation reactions, while offering insights into future research directions in this dynamic field.
{"title":"Metal species confined in metal-organic frameworks for CO2 hydrogenation: Synthesis, catalytic mechanisms, and future perspectives","authors":"Bailing Zhong , Jundie Hu , Xiaogang Yang , Yinying Shu , Yahui Cai , Chang Ming Li , Jiafu Qu","doi":"10.1016/S1872-2067(24)60177-4","DOIUrl":"10.1016/S1872-2067(24)60177-4","url":null,"abstract":"<div><h3>ABSTRACT</h3><div>Metal-organic frameworks (MOFs) serve as highly effective hosts for ultrasmall metal species, creating advanced nanocatalysts with superior catalytic performance, stability, and selective activity. The synergistic interplay between metal species confined within MOF nanopores and their active sites enhances catalytic efficiency in CO<sub>2</sub> hydrogenation reactions. Herein, recent advancements in synthesizing metal-confined MOFs are discussed, along with their applications in catalyzing CO<sub>2</sub> conversion through various methods such as photocatalysis, thermal catalysis, and photothermal catalysis. Additionally, we further emphasize the fundamental principles and factors that influence various types of catalytic CO<sub>2</sub> hydrogenation reactions, while offering insights into future research directions in this dynamic field.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"68 ","pages":"Pages 177-203"},"PeriodicalIF":15.7,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143094753","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)60185-3
Jinxin Wang, Jiaqi Zhang, Chen Chen
ABSTRACT
Electrochemical reduction of CO2 (CO2RR) to form high-energy-density and high-value-added multicarbon products has attracted much attention. Selective reduction of CO2 to C2+ products face the problems of low reaction rate, complex mechanism and low selectivity. Currently, except for a few examples, copper-based catalysts are the only option capable of achieving efficient generation of C2+ products. However, the continuous dynamic reconstruction of the catalyst causes great difficulty in understanding the structure-performance relationship of CO2RR. In this review, we first discuss the mechanism of C2+ product generation. The structural factors promoting C2+ product generation are outlined, and the dynamic evolution of these structural factors is discussed. Furthermore, the effects of electrolyte and electrolysis conditions are reviewed in a vision of dynamic surface. Finally, further exploration of the reconstruction mechanism of Cu-based catalysts and the application of emerging robotic AI chemists are discussed.
{"title":"Electrochemical CO2RR to C2+ products: A vision of dynamic surfaces of Cu-based catalysts","authors":"Jinxin Wang, Jiaqi Zhang, Chen Chen","doi":"10.1016/S1872-2067(24)60185-3","DOIUrl":"10.1016/S1872-2067(24)60185-3","url":null,"abstract":"<div><h3>ABSTRACT</h3><div>Electrochemical reduction of CO<sub>2</sub> (CO<sub>2</sub>RR) to form high-energy-density and high-value-added multicarbon products has attracted much attention. Selective reduction of CO<sub>2</sub> to C<sub>2+</sub> products face the problems of low reaction rate, complex mechanism and low selectivity. Currently, except for a few examples, copper-based catalysts are the only option capable of achieving efficient generation of C<sub>2+</sub> products. However, the continuous dynamic reconstruction of the catalyst causes great difficulty in understanding the structure-performance relationship of CO<sub>2</sub>RR. In this review, we first discuss the mechanism of C<sub>2+</sub> product generation. The structural factors promoting C<sub>2+</sub> product generation are outlined, and the dynamic evolution of these structural factors is discussed. Furthermore, the effects of electrolyte and electrolysis conditions are reviewed in a vision of dynamic surface. Finally, further exploration of the reconstruction mechanism of Cu-based catalysts and the application of emerging robotic AI chemists are discussed.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"68 ","pages":"Pages 83-102"},"PeriodicalIF":15.7,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143094754","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)60163-4
Yuqing Tang , Yanjun Chen , Aqsa Abid , Zichun Meng , Xiaoying Sun , Bo Li , Zhen Zhao
ABSTRACT
Recent studies have revealed the extraordinary performance of zirconium oxide in propane dehydrogenation, which is attributed to the excellent reactivity of the coordinatively unsaturated zirconium sites (Zrcus) around the oxygen vacancies. The origin of the enhanced catalytic activity of ZrO2 with defective tetrahedral Zr sites was examined by direct comparison with its pristine counterpart in the current study. Electronic-structure analysis revealed that electrons from oxygen removal were localized within vacancies on the defective surface, which directly attacked the C–H bond in propane. The involvement of localized electrons activates the C–H bond via back-donation to the antibonding orbital on the defective surface; conversely, charge is transferred from propane to the pristine surfaces. The barrier for the first C–H bond activation is clearly significantly reduced on the defective surfaces compared to that on the pristine surfaces, which verifies the superior activity of Zrcus. Notably, however, the desorption of both propene and hydrogen molecules from Zrcus is more difficult due to strong binding. The calculated turnover frequency (TOF) for propene formation demonstrates that the pristine surfaces exhibit better catalytic performance at lower temperatures, whereas the defective surfaces have a larger TOF at high temperatures. However, the rate-determining step and reaction order on the defective surface differ from those on the pristine surface, which corroborates that the catalysts follow different mechanisms. A further optimization strategy was proposed to address the remaining bottlenecks in propane dehydrogenation on zirconium oxide.
{"title":"Revisiting the origin of the superior performance of defective zirconium oxide catalysts in propane dehydrogenation: Double-edged oxygen vacancy","authors":"Yuqing Tang , Yanjun Chen , Aqsa Abid , Zichun Meng , Xiaoying Sun , Bo Li , Zhen Zhao","doi":"10.1016/S1872-2067(24)60163-4","DOIUrl":"10.1016/S1872-2067(24)60163-4","url":null,"abstract":"<div><h3>ABSTRACT</h3><div>Recent studies have revealed the extraordinary performance of zirconium oxide in propane dehydrogenation, which is attributed to the excellent reactivity of the coordinatively unsaturated zirconium sites (Zr<sub>cus</sub>) around the oxygen vacancies. The origin of the enhanced catalytic activity of ZrO<sub>2</sub> with defective tetrahedral Zr sites was examined by direct comparison with its pristine counterpart in the current study. Electronic-structure analysis revealed that electrons from oxygen removal were localized within vacancies on the defective surface, which directly attacked the C–H bond in propane. The involvement of localized electrons activates the C–H bond <em>via</em> back-donation to the antibonding orbital on the defective surface; conversely, charge is transferred from propane to the pristine surfaces. The barrier for the first C–H bond activation is clearly significantly reduced on the defective surfaces compared to that on the pristine surfaces, which verifies the superior activity of Zr<sub>cus</sub>. Notably, however, the desorption of both propene and hydrogen molecules from Zr<sub>cus</sub> is more difficult due to strong binding. The calculated turnover frequency (TOF) for propene formation demonstrates that the pristine surfaces exhibit better catalytic performance at lower temperatures, whereas the defective surfaces have a larger TOF at high temperatures. However, the rate-determining step and reaction order on the defective surface differ from those on the pristine surface, which corroborates that the catalysts follow different mechanisms. A further optimization strategy was proposed to address the remaining bottlenecks in propane dehydrogenation on zirconium oxide.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"68 ","pages":"Pages 272-281"},"PeriodicalIF":15.7,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143103408","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)60181-6
Shijie Li , Changjun You , Fang Yang , Guijie Liang , Chunqiang Zhuang , Xin Li
ABSTRACT
Inefficient photo-carrier separation and sluggish photoreaction dynamics appreciably undermine the photocatalytic decontamination efficacy of photocatalysts. Herein, an S-scheme Mn0.5Cd0.5S/Bi2MoO6 heterojunction with interfacial Mo–S chemical bond is designed as an efficient photocatalyst. In this integrated photosystem, Bi2MoO6 and Mn0.5Cd0.5S function as oxidation and reduction centers of Mn0.5Cd0.5S/Bi2MoO6 microspheres, respectively. Importantly, the unique charge transfer mechanism in the chemically bonded S-scheme heterojunction with Mo–S bond as atom-scale charge transport highway effectively inhibits the photocorrosion of Mn0.5Cd0.5S and the recombination of photo-generated electron-hole pairs, endowing Mn0.5Cd0.5S/Bi2MoO6 photocatalyst with excellent photocatalytic decontamination performance and stability. Besides, integration of Mn0.5Cd0.5S nanocrystals into Bi2MoO6 improves hydrophilicity, conducive to the photoreactions. Strikingly, compared with Mn0.5Cd0.5S and Bi2MoO6, the Mn0.5Cd0.5S/Bi2MoO6 unveils much augmented photoactivity in tetracycline eradication, among which Mn0.5Cd0.5S/Bi2MoO6-2 possesses the highest activity with the rate constant up to 0.0323 min–1, prominently outperforming other counterparts. This research offers a chemical bonding engineering combining with S-scheme heterojunction strategy for constructing extraordinary photocatalysts for environmental purification.
{"title":"Interfacial Mo–S bond modulated S-scheme Mn0.5Cd0.5S/Bi2MoO6 heterojunction for boosted photocatalytic removal of emerging organic contaminants","authors":"Shijie Li , Changjun You , Fang Yang , Guijie Liang , Chunqiang Zhuang , Xin Li","doi":"10.1016/S1872-2067(24)60181-6","DOIUrl":"10.1016/S1872-2067(24)60181-6","url":null,"abstract":"<div><h3>ABSTRACT</h3><div>Inefficient photo-carrier separation and sluggish photoreaction dynamics appreciably undermine the photocatalytic decontamination efficacy of photocatalysts. Herein, an S-scheme Mn<sub>0.5</sub>Cd<sub>0.5</sub>S/Bi<sub>2</sub>MoO<sub>6</sub> heterojunction with interfacial Mo–S chemical bond is designed as an efficient photocatalyst. In this integrated photosystem, Bi<sub>2</sub>MoO<sub>6</sub> and Mn<sub>0.5</sub>Cd<sub>0.5</sub>S function as oxidation and reduction centers of Mn<sub>0.5</sub>Cd<sub>0.5</sub>S/Bi<sub>2</sub>MoO<sub>6</sub> microspheres, respectively. Importantly, the unique charge transfer mechanism in the chemically bonded S-scheme heterojunction with Mo–S bond as atom-scale charge transport highway effectively inhibits the photocorrosion of Mn<sub>0.5</sub>Cd<sub>0.5</sub>S and the recombination of photo-generated electron-hole pairs, endowing Mn<sub>0.5</sub>Cd<sub>0.5</sub>S/Bi<sub>2</sub>MoO<sub>6</sub> photocatalyst with excellent photocatalytic decontamination performance and stability. Besides, integration of Mn<sub>0.5</sub>Cd<sub>0.5</sub>S nanocrystals into Bi<sub>2</sub>MoO<sub>6</sub> improves hydrophilicity, conducive to the photoreactions. Strikingly, compared with Mn<sub>0.5</sub>Cd<sub>0.5</sub>S and Bi<sub>2</sub>MoO<sub>6</sub>, the Mn<sub>0.5</sub>Cd<sub>0.5</sub>S/Bi<sub>2</sub>MoO<sub>6</sub> unveils much augmented photoactivity in tetracycline eradication, among which Mn<sub>0.5</sub>Cd<sub>0.5</sub>S/Bi<sub>2</sub>MoO<sub>6</sub>-2 possesses the highest activity with the rate constant up to 0.0323 min<sup>–1</sup>, prominently outperforming other counterparts. This research offers a chemical bonding engineering combining with S-scheme heterojunction strategy for constructing extraordinary photocatalysts for environmental purification.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"68 ","pages":"Pages 259-271"},"PeriodicalIF":15.7,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143094364","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)60179-8
Baijing Wu , Jinrui Li , Xiaoxue Luo , Jingtian Ni , Yiting Lu , Minhua Shao , Cunpu Li , Zidong Wei
ABSTRACT
The triple bond in N2 has an extremely high bond energy and is thus difficult to break. N2 is commonly converted into NH3 artificially via the Haber-Bosch process, and NH3 can be utilized to produce other nitrogen-containing chemicals. Here, we developed an electron catalyzed method to directly fix N2 into azos, by pushing and pulling the electron into and from the aromatic halide with the cyclic voltammetry method. The round-trip journey of electron can successfully weaken the triple bond in N2 through the electron pushing-induced aryl radical via a “brick trowel” transition state, and then produce the diazonium ions by pulling the electron out from the diazo radical intermediate. Different azos can be synthesized with this developed electron catalyzed approach. This approach provides a novel concept and practical route for the fixation of N2 at atmospheric pressure into chemical products valuable for industrial and commercial applications.
{"title":"A round-trip journey of electrons: Electron catalyzed direct fixation of N2 to azos","authors":"Baijing Wu , Jinrui Li , Xiaoxue Luo , Jingtian Ni , Yiting Lu , Minhua Shao , Cunpu Li , Zidong Wei","doi":"10.1016/S1872-2067(24)60179-8","DOIUrl":"10.1016/S1872-2067(24)60179-8","url":null,"abstract":"<div><h3>ABSTRACT</h3><div>The triple bond in N<sub>2</sub> has an extremely high bond energy and is thus difficult to break. N<sub>2</sub> is commonly converted into NH<sub>3</sub> artificially <em>via</em> the Haber-Bosch process, and NH<sub>3</sub> can be utilized to produce other nitrogen-containing chemicals. Here, we developed an electron catalyzed method to directly fix N<sub>2</sub> into azos, by pushing and pulling the electron into and from the aromatic halide with the cyclic voltammetry method. The round-trip journey of electron can successfully weaken the triple bond in N<sub>2</sub> through the electron pushing-induced aryl radical <em>via</em> a “brick trowel” transition state, and then produce the diazonium ions by pulling the electron out from the diazo radical intermediate. Different azos can be synthesized with this developed electron catalyzed approach. This approach provides a novel concept and practical route for the fixation of N<sub>2</sub> at atmospheric pressure into chemical products valuable for industrial and commercial applications.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"68 ","pages":"Pages 386-393"},"PeriodicalIF":15.7,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143094368","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)60158-0
Fei-Xiang Dong , Tian Jin , Xiaojuan Yu , Hong-Yue Wang , Qi Chen , Jian-He Xu , Gao-Wei Zheng
ABSTRACT
Chiral cyclic amino alcohols with contiguous stereocenters are key building blocks in the synthesis of bioactive molecules and pharmaceuticals. Artificial cascade biocatalysis represents an attractive method for the synthesis of chiral molecules bearing multiple stereocenters from readily available materials. Here we reported an artificial cascade biocatalysis comprising an epoxide hydrolase, an alcohol dehydrogenase, and a reductive aminase or an amine dehydrogenase. It can be utilized to access all four stereoisomers of 2-aminocyclohexanol with two contiguous stereocenters in high yields (up to 95%) and excellent stereoselectivity (up to 98% de) starting from readily available cyclohexene oxide without isolation of the intermediates. Additionally, the biocatalytic cascade has been successfully extended to the production of structurally diverse 2-(alkylamino)cyclohexanols by replacing ammonia with different organic amines.
{"title":"Artificial cascade biocatalysis for the synthesis of 2-aminocyclohexanols with contiguous stereocenters","authors":"Fei-Xiang Dong , Tian Jin , Xiaojuan Yu , Hong-Yue Wang , Qi Chen , Jian-He Xu , Gao-Wei Zheng","doi":"10.1016/S1872-2067(24)60158-0","DOIUrl":"10.1016/S1872-2067(24)60158-0","url":null,"abstract":"<div><h3>ABSTRACT</h3><div>Chiral cyclic amino alcohols with contiguous stereocenters are key building blocks in the synthesis of bioactive molecules and pharmaceuticals. Artificial cascade biocatalysis represents an attractive method for the synthesis of chiral molecules bearing multiple stereocenters from readily available materials. Here we reported an artificial cascade biocatalysis comprising an epoxide hydrolase, an alcohol dehydrogenase, and a reductive aminase or an amine dehydrogenase. It can be utilized to access all four stereoisomers of 2-aminocyclohexanol with two contiguous stereocenters in high yields (up to 95%) and excellent stereoselectivity (up to 98% <em>de</em>) starting from readily available cyclohexene oxide without isolation of the intermediates. Additionally, the biocatalytic cascade has been successfully extended to the production of structurally diverse 2-(alkylamino)cyclohexanols by replacing ammonia with different organic amines.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"68 ","pages":"Pages 345-355"},"PeriodicalIF":15.7,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143103363","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)60170-1
Baofei Hao , Younes Ahmadi , Jan Szulejko , Tianhao Zhang , Zhansheng Lu , Ki-Hyun Kim
ABSTRACT
It is a challenging task to efficiently convert deleterious hydrogen sulfide (H2S) into less harmful products such as SO42– species. In an effort to address such issue, a step-scheme (S-scheme) heterojunction photocatalyst has been built by concatenating TiO2 (P25) and ultrathin Bi4O5Br2 into TiO2/Bi4O5Br2 (namely, x-TB-y: x and y denote the molar ratio of TiO2:Bi4O5Br2 and pH value for solution-based synthesis, respectively) via in-situ hydrothermal method. The S-scheme charge transfer pathway in TB is confirmed by electron spin resonance and band structure analysis while experimental data and density functional theory calculations suggest the formation of an internal electric field to facilitate the separation and transfer of photoinduced charge carriers. Accordingly, the optimized heterojunction photocatalyst, i.e., 5-TB-9, showcases significantly high (> 99%) removal efficiency against 10 ppm H2S in a 17 L chamber within 12 minutes (removal kinetic rate r: 0.7 mmol·h–1·g–1, specific clean air delivery rate SCADR: 5554 L·h–1·g–1, quantum yield QY: 3.24 E-3 molecules·photon–1, and space-time yield STY: 3.24 E-3 molecules·photon–1·mg–1). Combined analysis of in-situ diffuse reflectance infrared Fourier transform adsorption spectra and gas chromatography-mass spectrometry allows to evaluate the mechanisms leading to the complete degradation of H2S (i.e., into SO42– without forming any intermediate species). This work demonstrates the promising remediation potential of an S-scheme TiO2/Bi4O5Br2 photocatalyst against hazardous H2S gas for sustainable environmental remediation.
{"title":"The design and fabrication of TiO2/Bi4O5Br2 step-scheme heterojunctions for the photodegradation of gaseous hydrogen sulfide: DFT calculation, kinetics, pathways, and mechanisms","authors":"Baofei Hao , Younes Ahmadi , Jan Szulejko , Tianhao Zhang , Zhansheng Lu , Ki-Hyun Kim","doi":"10.1016/S1872-2067(24)60170-1","DOIUrl":"10.1016/S1872-2067(24)60170-1","url":null,"abstract":"<div><h3>ABSTRACT</h3><div>It is a challenging task to efficiently convert deleterious hydrogen sulfide (H<sub>2</sub>S) into less harmful products such as SO<sub>4</sub><sup>2–</sup> species. In an effort to address such issue, a step-scheme (S-scheme) heterojunction photocatalyst has been built by concatenating TiO<sub>2</sub> (P25) and ultrathin Bi<sub>4</sub>O<sub>5</sub>Br<sub>2</sub> into TiO<sub>2</sub>/Bi<sub>4</sub>O<sub>5</sub>Br<sub>2</sub> (namely, <em>x</em>-TB-<em>y</em>: <em>x</em> and <em>y</em> denote the molar ratio of TiO<sub>2</sub>:Bi<sub>4</sub>O<sub>5</sub>Br<sub>2</sub> and pH value for solution-based synthesis, respectively) <em>via in-situ</em> hydrothermal method. The S-scheme charge transfer pathway in TB is confirmed by electron spin resonance and band structure analysis while experimental data and density functional theory calculations suggest the formation of an internal electric field to facilitate the separation and transfer of photoinduced charge carriers. Accordingly, the optimized heterojunction photocatalyst, i.e., 5-TB-9, showcases significantly high (> 99%) removal efficiency against 10 ppm H<sub>2</sub>S in a 17 L chamber within 12 minutes (removal kinetic rate <em>r</em>: 0.7 mmol·h<sup>–1</sup>·g<sup>–1</sup>, specific clean air delivery rate SCADR: 5554 L·h<sup>–1</sup>·g<sup>–1</sup>, quantum yield QY: 3.24 E-3 molecules·photon<sup>–1</sup>, and space-time yield STY: 3.24 E-3 molecules·photon<sup>–1</sup>·mg<sup>–1</sup>). Combined analysis of <em>in-situ</em> diffuse reflectance infrared Fourier transform adsorption spectra and gas chromatography-mass spectrometry allows to evaluate the mechanisms leading to the complete degradation of H<sub>2</sub>S (i.e., into SO<sub>4</sub><sup>2–</sup> without forming any intermediate species). This work demonstrates the promising remediation potential of an S-scheme TiO<sub>2</sub>/Bi<sub>4</sub>O<sub>5</sub>Br<sub>2</sub> photocatalyst against hazardous H<sub>2</sub>S gas for sustainable environmental remediation.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"68 ","pages":"Pages 282-299"},"PeriodicalIF":15.7,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143094363","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)60166-X
Neng Gong , Quanzheng Deng , Yujiao Wang , Zitao Wang , Lu Han , Peng Wu , Shun'ai Che
ABSTRACT
Designing Fischer-Tropsch synthesis (FTS) catalysts to selectively produce liquid hydrocarbon fuels is a crucial challenge. Herein, we selectively introduced Co nanoparticles (NPs) into the micropores and mesopores of an ordered mesoporous MFI zeolite (OMMZ) through impregnation, which controlled the carbon number distribution in the FTS products by tuning the position of catalytic active sites in differently sized pores. The Co precursors coordinated by acetate with a size of 9.4 × 4.2 × 2.5 Å and by 2,2‘-bipyridine with a size of 9.5 × 8.7 × 7.9 Å, smaller and larger than the micropores (ca. 5.5 Å) of MFI, made the Co species incorporated in OMMZ's micropores and mesopores, respectively. The carbon number products synthesized with the Co NPs confined in mesopores were larger than that in micropores. The high jet and diesel selectivities of 66.5% and 65.3% were achieved with Co NPs confined in micropores and mesopores of less acidic Na-type OMMZ, respectively. Gasoline and jet selectivities of 76.7% and 70.8% were achieved with Co NPs confined in micropores and mesopores of H-type OMMZ with Brönsted acid sites, respectively. A series of characterizations revealed that the selective production of diesel and jet fuels was due to the C–C cleavage suppressing of heavier hydrocarbons by the Co NPs located in mesopores.
{"title":"Co nanoparticles confined in mesopores of MFI zeolite for selective syngas conversion to heavy liquid hydrocarbon fuels","authors":"Neng Gong , Quanzheng Deng , Yujiao Wang , Zitao Wang , Lu Han , Peng Wu , Shun'ai Che","doi":"10.1016/S1872-2067(24)60166-X","DOIUrl":"10.1016/S1872-2067(24)60166-X","url":null,"abstract":"<div><h3>ABSTRACT</h3><div>Designing Fischer-Tropsch synthesis (FTS) catalysts to selectively produce liquid hydrocarbon fuels is a crucial challenge. Herein, we selectively introduced Co nanoparticles (NPs) into the micropores and mesopores of an ordered mesoporous <strong>MFI</strong> zeolite (OMMZ) through impregnation, which controlled the carbon number distribution in the FTS products by tuning the position of catalytic active sites in differently sized pores. The Co precursors coordinated by acetate with a size of 9.4 × 4.2 × 2.5 Å and by 2,2<em>‘</em>-bipyridine with a size of 9.5 × 8.7 × 7.9 Å, smaller and larger than the micropores (<em>ca.</em> 5.5 Å) of <strong>MFI</strong>, made the Co species incorporated in OMMZ's micropores and mesopores, respectively. The carbon number products synthesized with the Co NPs confined in mesopores were larger than that in micropores. The high jet and diesel selectivities of 66.5% and 65.3% were achieved with Co NPs confined in micropores and mesopores of less acidic Na-type OMMZ, respectively. Gasoline and jet selectivities of 76.7% and 70.8% were achieved with Co NPs confined in micropores and mesopores of H-type OMMZ with Brönsted acid sites, respectively. A series of characterizations revealed that the selective production of diesel and jet fuels was due to the C–C cleavage suppressing of heavier hydrocarbons by the Co NPs located in mesopores.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"68 ","pages":"Pages 246-258"},"PeriodicalIF":15.7,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143094366","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)60162-2
Liyuan Gong , Li Tao , Lei Wang , Xian-Zhu Fu , Shuangyin Wang
ABSTRACT
Investigating highly effective electrocatalysts for high-temperature proton exchange membrane fuel cells (HT-PEMFC) requires the resistance to phosphate acid (PA) poisoning at cathodic oxygen reduction reaction (ORR). Recent advancements in catalysts have focused on alleviating phosphoric anion adsorption on Pt-based catalysts with modified electronic structure or catalytic interface and developing Fe-N-C based catalysts with immunity of PA poisoning. Fe-N-C-based catalysts have emerged as promising alternatives to Pt-based catalysts, offering significant potential to overcome the characteristic adsorption of phosphate anion on Pt. An overview of these developments provides insights into catalytic mechanisms and facilitates the design of more efficient catalysts. This review begins with an exploration of basic poisoning principles, followed by a critical summary of characterization techniques employed to identified the underlying mechanism of poisoning effect. Attention is then directed to endeavors aimed at enhancing the HT-PEMFC performance by well-designed catalysts. Finally, the opportunities and challenges in developing the anti-PA poisoning strategy and practical HT-PEMFC is discussed. Through these discussions, a comprehensive understanding of PA-poisoning bottlenecks and inspire future research directions is aim to provided.
{"title":"Focus on the catalysts to resist the phosphate poisoning in high-temperature proton exchange membrane fuel cells","authors":"Liyuan Gong , Li Tao , Lei Wang , Xian-Zhu Fu , Shuangyin Wang","doi":"10.1016/S1872-2067(24)60162-2","DOIUrl":"10.1016/S1872-2067(24)60162-2","url":null,"abstract":"<div><h3>ABSTRACT</h3><div>Investigating highly effective electrocatalysts for high-temperature proton exchange membrane fuel cells (HT-PEMFC) requires the resistance to phosphate acid (PA) poisoning at cathodic oxygen reduction reaction (ORR). Recent advancements in catalysts have focused on alleviating phosphoric anion adsorption on Pt-based catalysts with modified electronic structure or catalytic interface and developing Fe-N-C based catalysts with immunity of PA poisoning. Fe-N-C-based catalysts have emerged as promising alternatives to Pt-based catalysts, offering significant potential to overcome the characteristic adsorption of phosphate anion on Pt. An overview of these developments provides insights into catalytic mechanisms and facilitates the design of more efficient catalysts. This review begins with an exploration of basic poisoning principles, followed by a critical summary of characterization techniques employed to identified the underlying mechanism of poisoning effect. Attention is then directed to endeavors aimed at enhancing the HT-PEMFC performance by well-designed catalysts. Finally, the opportunities and challenges in developing the anti-PA poisoning strategy and practical HT-PEMFC is discussed. Through these discussions, a comprehensive understanding of PA-poisoning bottlenecks and inspire future research directions is aim to provided.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"68 ","pages":"Pages 155-176"},"PeriodicalIF":15.7,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143094752","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)60186-5
Lin Dong , Zhiqiang Fang , Qianbo Yuan , Yong Fan , Yong Yang , Ping Wang , Shixiong Sheng , Yanqin Wang , Zupeng Chen
ABSTRACT
Many strategies have been proposed to produce arenes from lignin as liquid fuel additives. However, the development of these methods is limited by the low yield of products, low atom utilization, and inefficient lignin depolymerization. Herein, we develop an energy-efficient synthetic method for the production of high-carbon-number arenes from sustainable lignin with a total yield of 23.1 wt%. Particularly, high carbon number arenes are obtained by fully utilizing the formaldehyde stabilizing additive and the methoxy group in lignin. The process begins with the reductive depolymerization of formaldehyde-stabilized lignin, followed by transmethylation between lignin monomers over Au/Nb2O5 catalyst, and the Ru/Nb2O5-catalyzed hydrodeoxygenation. This work demonstrates the potential of value-added arenes production directly from lignin.
{"title":"Selective utilization of formaldehyde stabilizing additive and methoxy groups in lignin for the production of high-carbon-number arenes","authors":"Lin Dong , Zhiqiang Fang , Qianbo Yuan , Yong Fan , Yong Yang , Ping Wang , Shixiong Sheng , Yanqin Wang , Zupeng Chen","doi":"10.1016/S1872-2067(24)60186-5","DOIUrl":"10.1016/S1872-2067(24)60186-5","url":null,"abstract":"<div><h3>ABSTRACT</h3><div>Many strategies have been proposed to produce arenes from lignin as liquid fuel additives. However, the development of these methods is limited by the low yield of products, low atom utilization, and inefficient lignin depolymerization. Herein, we develop an energy-efficient synthetic method for the production of high-carbon-number arenes from sustainable lignin with a total yield of 23.1 wt%. Particularly, high carbon number arenes are obtained by fully utilizing the formaldehyde stabilizing additive and the methoxy group in lignin. The process begins with the reductive depolymerization of formaldehyde-stabilized lignin, followed by transmethylation between lignin monomers over Au/Nb<sub>2</sub>O<sub>5</sub> catalyst, and the Ru/Nb<sub>2</sub>O<sub>5</sub>-catalyzed hydrodeoxygenation. This work demonstrates the potential of value-added arenes production directly from lignin.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"68 ","pages":"Pages 356-365"},"PeriodicalIF":15.7,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143103362","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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