Applied Catalysis A: General最新文献

英文中文

Uniform and fully exposed Rh clusters on defect-rich CeO2 enable efficient catalytic N2O decomposition

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-01-21 DOI: 10.1016/j.apcata.2025.120122

Shidong Bao , Xuxing Lu , Le Yu , Yejin Song , Heyun Fu , Xiaolei Qu , Jeong Young Park , Shourong Zheng

Precise construction of single and uniform active species in supported noble metal catalysts, for clarifying structure-activity relationships and optimizing catalytic activity, is essential but highly challenging. Here we have developed a defects-assisted adsorption combined with hydrogen-induced aggregation method for controllably fabricating uniform Rh species from single atoms to nanoclusters (1.1 nm) and ultrafine nanoparticles (2.1 nm) on defect-rich CeO₂. For catalytic N₂O decomposition, Rh nanocluster catalysts with nearly 100 % Rh exposure present superior activity, with a turnover frequency (137.4 h⁻¹ at 250 °C) 4.6 times higher than Rh nanoparticles catalysts and 148.8 times higher than Rh single atoms catalysts. Mechanism studies indicate different Rh species on the defect-rich CeO₂ have various responses to O₂, mainly due to electronic effect. Rh clusters act as the optimal active species owing to the presence of adjacent Rh atoms and positively charged Rh species, facilitating the transformation of intermediates and desorption of products, respectively. Besides, defects from CeO₂ nanorods play crucial roles in the controlled catalyst synthesis process and the enhancement of catalytic activity. This work highlights that precisely constructing metal active sites with single-cluster species and appropriate electronic properties can achieve optimal catalytic performance in some structure-sensitive reactions.

{"title":"Uniform and fully exposed Rh clusters on defect-rich CeO2 enable efficient catalytic N2O decomposition","authors":"Shidong Bao , Xuxing Lu , Le Yu , Yejin Song , Heyun Fu , Xiaolei Qu , Jeong Young Park , Shourong Zheng","doi":"10.1016/j.apcata.2025.120122","DOIUrl":"10.1016/j.apcata.2025.120122","url":null,"abstract":"<div><div>Precise construction of single and uniform active species in supported noble metal catalysts, for clarifying structure-activity relationships and optimizing catalytic activity, is essential but highly challenging. Here we have developed a defects-assisted adsorption combined with hydrogen-induced aggregation method for controllably fabricating uniform Rh species from single atoms to nanoclusters (1.1 nm) and ultrafine nanoparticles (2.1 nm) on defect-rich CeO2. For catalytic N2O decomposition, Rh nanocluster catalysts with nearly 100 % Rh exposure present superior activity, with a turnover frequency (137.4 h−1 at 250 °C) 4.6 times higher than Rh nanoparticles catalysts and 148.8 times higher than Rh single atoms catalysts. Mechanism studies indicate different Rh species on the defect-rich CeO2 have various responses to O2, mainly due to electronic effect. Rh clusters act as the optimal active species owing to the presence of adjacent Rh atoms and positively charged Rh species, facilitating the transformation of intermediates and desorption of products, respectively. Besides, defects from CeO2 nanorods play crucial roles in the controlled catalyst synthesis process and the enhancement of catalytic activity. This work highlights that precisely constructing metal active sites with single-cluster species and appropriate electronic properties can achieve optimal catalytic performance in some structure-sensitive reactions.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"693 ","pages":"Article 120122"},"PeriodicalIF":4.7,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143099868","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}

引用次数: 0

Effect of citric acid modification on denitration performance of CeO2-WO3/TiO2 catalyst

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-01-20 DOI: 10.1016/j.apcata.2025.120121

Yuming Yang , Xue Bian , Feng Xie , Yuting Bai

This study investigates the performance regulation and mechanism of citric acid on the CeO₂-WO₃/TiO₂ catalyst. The CeO₂-WO₃/TiO₂-6 % catalyst exhibits a denitrification conversion rate exceeding 90 % within the temperature range of 217–517°C, with a significantly broader working temperature window. Additionally, it demonstrates excellent N₂ selectivity and superior resistance to water and sulfur. Through a series of characterization methods, the physical and chemical properties of the catalyst were analyzed. The results indicate that the complexation of an appropriate amount of citric acid with Ce and W can refine the grain size, increase the specific surface area, and provide more acidic sites, significantly improving the adsorption properties. Moreover, the addition of citric acid during the preparation process can promote the electron transfer between active elements, increase the oxygen vacancy content, and enhance the catalyst's redox properties.

引用次数: 0

Mesostructured carbon nitride synthesized by NaOH-assisted detemplation for enhanced catalytic synthesis of dimethyl carbonate from ethylene carbonate

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-01-17 DOI: 10.1016/j.apcata.2025.120120

Xue-Wen Zhang, Jing-Yun Xu, Zhou-Hong Yu, Fei Wang, Jie Xu , Bing Xue

Dimethyl carbonate (DMC) is an important building block in modern chemical synthesis, and the transesterification reaction between ethylene carbonate (EC) and CH₃OH has been widely regarded as one of the most promising routes for the synthesis of DMC. Herein, a series of mesoporous carbon nitride (mpg-C₃N₄-x) materials were synthesized through a hard-templating method, adopting NaOH (a.q.) as a facile detemplating agent. Compared with the mpg-C₃N₄-F material prepared using traditional corrosive NH₄HF₂ (a.q.) as the detemplating agent, the mpg-C₃N₄-x materials possessed higher percentages of active bridging nitrogen species. Under optimal reaction conditions, the conversion of EC and selectivity to DMC achieved in mpg-C₃N₄ were up to 81.2 % and 99.9 %. The utilization of NaOH (a.q.) could alter the distributions of nitrogen species and enhance the alkaline strength of mpg-C₃N₄. As metal-free heterogeneous catalysts, the mpg-C₃N₄-x materials showed good recyclability and versatility for the transesterification reactions of various substrates.

{"title":"Mesostructured carbon nitride synthesized by NaOH-assisted detemplation for enhanced catalytic synthesis of dimethyl carbonate from ethylene carbonate","authors":"Xue-Wen Zhang, Jing-Yun Xu, Zhou-Hong Yu, Fei Wang, Jie Xu , Bing Xue","doi":"10.1016/j.apcata.2025.120120","DOIUrl":"10.1016/j.apcata.2025.120120","url":null,"abstract":"<div><div>Dimethyl carbonate (DMC) is an important building block in modern chemical synthesis, and the transesterification reaction between ethylene carbonate (EC) and CH3OH has been widely regarded as one of the most promising routes for the synthesis of DMC. Herein, a series of mesoporous carbon nitride (mpg-C3N4-x) materials were synthesized through a hard-templating method, adopting NaOH (a.q.) as a facile detemplating agent. Compared with the mpg-C3N4-F material prepared using traditional corrosive NH4HF2 (a.q.) as the detemplating agent, the mpg-C3N4-x materials possessed higher percentages of active bridging nitrogen species. Under optimal reaction conditions, the conversion of EC and selectivity to DMC achieved in mpg-C3N4 were up to 81.2 % and 99.9 %. The utilization of NaOH (a.q.) could alter the distributions of nitrogen species and enhance the alkaline strength of mpg-C3N4. As metal-free heterogeneous catalysts, the mpg-C3N4-x materials showed good recyclability and versatility for the transesterification reactions of various substrates.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"693 ","pages":"Article 120120"},"PeriodicalIF":4.7,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143099825","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}

引用次数: 0

Ni2P-CoxP/U-ZrO2/C NFs heterojunction photocatalyst for efficient and stable degradation of PET waste under visible light

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-01-17 DOI: 10.1016/j.apcata.2025.120119

Wenbin Qu , Lixin Song , Guixiang Peng , Xiaoli Shao , Yang Wang , Pingfan Du , Jie Xiong

Petroleum-derived PET plastics and fibers are widely used in packaging and textile fields due to their superior properties and have become a major source of plastic waste. In this study, Ni₂P-Co_xP/ZrO₂/C NFs p-n heterojunction photocatalytic system with the UiO-66-NH₂ metal-organic backbone (MOFs)-derived ZrO₂ (U-ZrO₂) was constructed by a combined method of electrospinning, carbonization, hydrothermal, and phosphorization process. Carbon nanofibers are used as carriers to combine the different components effectively. The Ni₂P-Co_xP/U-ZrO₂/C NFs show strong light absorption ability throughout the entire visible light region. The needle-shaped structure of Ni₂P-Co_xP can provide abundant active sites, increase the reflection of light on the fiber surface, and promote the utilization of light by the photocatalyst. With the incorporation of the MOF structure, the specific surface area of the fibers was greatly enhanced. The coupling of Co_xP with Ni₂P and U-ZrO₂ establishes a p-n heterojunction at the photocatalytic interface, which promotes the separation efficiency of photogenerated carriers and prolongs the charge lifetime while maintaining the strong redox capacity of the catalyst, enhancing the photocatalytic degradation activity. The MOF-derived ZrO₂ still maintains an octahedral shape, which favors the attachment of Ni₂P and Co_xP. As a result, the hydrogen production of the system reached 303.64

μ mo l_{H_{2}} g_{Sub}^{- 1}

after 24 h, and the weight loss rate of PET reached 18.77 ± 4.28 %. Besides, the reusability of the catalyst was greatly improved by re-phosphorization of the used catalyst, which enables it to recover its catalytic degradation efficiency. This work provides new insights into the rational design of heterojunction photocatalysts with superior degradation performance.

{"title":"Ni2P-CoxP/U-ZrO2/C NFs heterojunction photocatalyst for efficient and stable degradation of PET waste under visible light","authors":"Wenbin Qu , Lixin Song , Guixiang Peng , Xiaoli Shao , Yang Wang , Pingfan Du , Jie Xiong","doi":"10.1016/j.apcata.2025.120119","DOIUrl":"10.1016/j.apcata.2025.120119","url":null,"abstract":"<div><div>Petroleum-derived PET plastics and fibers are widely used in packaging and textile fields due to their superior properties and have become a major source of plastic waste. In this study, Ni2P-CoxP/ZrO2/C NFs p-n heterojunction photocatalytic system with the UiO-66-NH2 metal-organic backbone (MOFs)-derived ZrO2 (U-ZrO2) was constructed by a combined method of electrospinning, carbonization, hydrothermal, and phosphorization process. Carbon nanofibers are used as carriers to combine the different components effectively. The Ni2P-CoxP/U-ZrO2/C NFs show strong light absorption ability throughout the entire visible light region. The needle-shaped structure of Ni2P-CoxP can provide abundant active sites, increase the reflection of light on the fiber surface, and promote the utilization of light by the photocatalyst. With the incorporation of the MOF structure, the specific surface area of the fibers was greatly enhanced. The coupling of CoxP with Ni2P and U-ZrO2 establishes a p-n heterojunction at the photocatalytic interface, which promotes the separation efficiency of photogenerated carriers and prolongs the charge lifetime while maintaining the strong redox capacity of the catalyst, enhancing the photocatalytic degradation activity. The MOF-derived ZrO2 still maintains an octahedral shape, which favors the attachment of Ni2P and CoxP. As a result, the hydrogen production of the system reached 303.64 <math><mrow><mtext>μ</mtext><mtext>mo</mtext><msub><mrow><mtext>l</mtext></mrow><mrow><msub><mrow><mtext>H</mtext></mrow><mrow><mn>2</mn></mrow></msub></mrow></msub><msubsup><mrow><mtext>g</mtext></mrow><mrow><mtext>Sub</mtext></mrow><mrow><mo>−</mo><mn>1</mn></mrow></msubsup></mrow></math> after 24 h, and the weight loss rate of PET reached 18.77 ± 4.28 %. Besides, the reusability of the catalyst was greatly improved by re-phosphorization of the used catalyst, which enables it to recover its catalytic degradation efficiency. This work provides new insights into the rational design of heterojunction photocatalysts with superior degradation performance.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"693 ","pages":"Article 120119"},"PeriodicalIF":4.7,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143099830","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}

引用次数: 0

Formation of Lewis acid-base pairs between carboxyl grafted ZnxCd1-xS and imine COF enhance hydrogen production under visible light

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-01-13 DOI: 10.1016/j.apcata.2025.120118

Jingzhi Wang, Mei Li, Nini Zhao, Zhiliang Jin

Directed charge transfer is an effective way to improve charge utilization efficiency and promote photocatalytic hydrogen evolution reactions. This article reports the formation of a Lewis acid-base catalytic system using carboxyl-modified Zn_xCd_1-xS and imine COF (2,4,6-tris (4-aminophenyl) triazine and tris (4-formylphenyl) amine under Schiff base to form imine COF). Under visible light irradiation, the optimum hydrogen production activity of Zn_xCd_1-xS/COF (3:20 (mass ratio)) can reach 6.65 mmol·g⁻¹·h⁻¹. It is twice as that of high as pure Zn_xCd_1-xS and exhibits good photocatalytic hydrogen evolution stability. In the presence of Lewis acid-base pairs, directional charge transfer is successfully achieved, thereby increasing charge utilization and enhancing photocatalytic hydrogen evolution. In addition, 2D sheet-like COFs have played a good dispersing role for Zn_xCd_1-xS, reducing the problem of low active sites caused by aggregation of Zn_xCd_1-xS, and also contributing to the improvement of photocatalytic activity. This work paves the way for the construction of COFs and the implementation of charge guidance using Lewis acid-base pairs.

{"title":"Formation of Lewis acid-base pairs between carboxyl grafted ZnxCd1-xS and imine COF enhance hydrogen production under visible light","authors":"Jingzhi Wang, Mei Li, Nini Zhao, Zhiliang Jin","doi":"10.1016/j.apcata.2025.120118","DOIUrl":"10.1016/j.apcata.2025.120118","url":null,"abstract":"<div><div>Directed charge transfer is an effective way to improve charge utilization efficiency and promote photocatalytic hydrogen evolution reactions. This article reports the formation of a Lewis acid-base catalytic system using carboxyl-modified ZnxCd1-xS and imine COF (2,4,6-tris (4-aminophenyl) triazine and tris (4-formylphenyl) amine under Schiff base to form imine COF). Under visible light irradiation, the optimum hydrogen production activity of ZnxCd1-xS/COF (3:20 (mass ratio)) can reach 6.65 mmol·g−1·h−1. It is twice as that of high as pure ZnxCd1-xS and exhibits good photocatalytic hydrogen evolution stability. In the presence of Lewis acid-base pairs, directional charge transfer is successfully achieved, thereby increasing charge utilization and enhancing photocatalytic hydrogen evolution. In addition, 2D sheet-like COFs have played a good dispersing role for ZnxCd1-xS, reducing the problem of low active sites caused by aggregation of ZnxCd1-xS, and also contributing to the improvement of photocatalytic activity. This work paves the way for the construction of COFs and the implementation of charge guidance using Lewis acid-base pairs.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"693 ","pages":"Article 120118"},"PeriodicalIF":4.7,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143099826","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}

引用次数: 0

Effects of preparation methods on Ru-based catalysts for CO hydrogenation to olefins

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-01-12 DOI: 10.1016/j.apcata.2025.120117

Jiaqi Li , Xuan Zhou , Huachen Shen , Ruitao Li , Tiejun Lin , Yunlei An , Liangshu Zhong

The influence of impregnation sequences on the structure and performance of the Ru-based catalysts for olefins synthesis from syngas via Fischer-Tropsch reaction (FTO) was investigated. Among the catalysts studied, Na-Ru/SiO₂ (Na was impregnated before Ru) exhibited the highest CO conversion (43.5 %) and olefins yield (33.9 %). In contrast, Ru-Na/SiO₂ (Ru was impregnated before Na) showed the lowest CO conversion (26.6 %) and olefins yield (19.8 %). Characterization analysis indicated that Na-Ru/SiO₂ exhibited higher Ru dispersion. In addition, the structural configuration of Na-Ru/SiO₂ was found to enhance CO adsorption capabilities to create a C*-rich localized chemical environment, thereby increasing catalytic activity and olefins production. This study demonstrates a straightforward and effective approach to optimize Ru utilization for the design of Ru-based FTO catalysts.

引用次数: 0

Modulation of electronic metal-support interaction (EMSI) in Cu-ZnO/ZrO2 for isobutanol synthesis

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-01-11 DOI: 10.1016/j.apcata.2025.120114

Enjuan Ma , Min Tian , Jing Liu , Aoxiang Guo , Wei Huang , Qian Zhang

Modulating electronic metal-support interaction (EMSI) has been considered an effective strategy to improve the activity and selectivity of supported catalysts. The contributions of ZrO₂ crystalline phases to the EMSI of the Cu-ZnO/ZrO₂ were investigated in this paper. Results confirmed that the EMSI between Cu-ZnO and ZrO₂ became stronger with the ZrO₂ transformed from amorphous into tetragonal, which facilitated electron transfer from ZrO₂ to Cu and ZnO and promoted the adsorption of non-dissociative CO and the formation of the C-C coupling site, resulting in the highest selectivity of total alcohol (48.52 %) and isobutanol yield (22.18 g·L⁻¹·h⁻¹). The isobutanol synthesis mechanism was further revealed by in situ DRIFTS: Oxygen vacancy sites and Cu⁰ sites responsible for the generation of CH_xO* (CO* or HCOO*) and CH_x*, respectively, which were coupled at the Zn^δ+ (0 <δ<2) sites to generate C₂ oxygenated intermediate, followed immediately by a rapid two-step β-addition to generate isobutanol.

{"title":"Modulation of electronic metal-support interaction (EMSI) in Cu-ZnO/ZrO2 for isobutanol synthesis","authors":"Enjuan Ma , Min Tian , Jing Liu , Aoxiang Guo , Wei Huang , Qian Zhang","doi":"10.1016/j.apcata.2025.120114","DOIUrl":"10.1016/j.apcata.2025.120114","url":null,"abstract":"<div><div>Modulating electronic metal-support interaction (EMSI) has been considered an effective strategy to improve the activity and selectivity of supported catalysts. The contributions of ZrO2 crystalline phases to the EMSI of the Cu-ZnO/ZrO2 were investigated in this paper. Results confirmed that the EMSI between Cu-ZnO and ZrO2 became stronger with the ZrO2 transformed from amorphous into tetragonal, which facilitated electron transfer from ZrO2 to Cu and ZnO and promoted the adsorption of non-dissociative CO and the formation of the C-C coupling site, resulting in the highest selectivity of total alcohol (48.52 %) and isobutanol yield (22.18 g·L−1·h−1). The isobutanol synthesis mechanism was further revealed by in situ DRIFTS: Oxygen vacancy sites and Cu0 sites responsible for the generation of CHxO* (CO* or HCOO*) and CHx*, respectively, which were coupled at the Znδ+ (0 <δ<2) sites to generate C2 oxygenated intermediate, followed immediately by a rapid two-step β-addition to generate isobutanol.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"692 ","pages":"Article 120114"},"PeriodicalIF":4.7,"publicationDate":"2025-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143136833","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}

引用次数: 0

Constructed Pt active domain to catalyze acetylene hydrochlorination efficiently

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-01-10 DOI: 10.1016/j.apcata.2025.120113

Chengkun Wu , Guohui Jiang , Haixia Liang , Jian Li , Yaqiong Su , Wenchao Yang , Jinli Zhang

In industry, liquid acetone is commonly used to store acetylene. The oxygen atoms in acetone molecules are more electronegative, whereas the C atoms in acetylene molecules are more electronegative, creating an electrical difference that results in electrostatic interactions between acetone and acetylene molecules. This interaction enhances the intermolecular forces between acetone and acetylene, suggesting that the presence of a CO structure may promote the adsorption and activation of acetylene molecules. In this study, a series of phenyl-based ligands containing X = O (X = C, N, S, and P) structures were used to prepare Pt-L_x/AC catalysts via the impregnation method. Performance evaluation revealed that the Pt-L₅/AC catalyst, with 4-nitrosophenol (L₅) as the ligand, exhibited the best catalytic performance. System characterization and theoretical calculations indicated that the N = O structure in the L₅ ligand enhances the electronic structure of the catalyst’s active center, while the benzene ring further optimizes the catalytic reaction microenvironment. Theoretical results also show that H₂PtCl₆ molecules with 4-nitrosophenol ligands have significant advantages in acetylene hydrochlorination kinetics, likely due to the dispersion of the electron density of the Pt core by the L₅ ligands. The addition of chlorine atoms to the CC bond of C₂H₂ molecules releases a substantial amount of energy, making the reaction irreversible and more thermodynamically favorable, and by using HCL molecules to dynamically compensate the active domain of Pt-based catalyst, the performance of Pt-based catalyst can be improved.

{"title":"Constructed Pt active domain to catalyze acetylene hydrochlorination efficiently","authors":"Chengkun Wu , Guohui Jiang , Haixia Liang , Jian Li , Yaqiong Su , Wenchao Yang , Jinli Zhang","doi":"10.1016/j.apcata.2025.120113","DOIUrl":"10.1016/j.apcata.2025.120113","url":null,"abstract":"<div><div>In industry, liquid acetone is commonly used to store acetylene. The oxygen atoms in acetone molecules are more electronegative, whereas the C atoms in acetylene molecules are more electronegative, creating an electrical difference that results in electrostatic interactions between acetone and acetylene molecules. This interaction enhances the intermolecular forces between acetone and acetylene, suggesting that the presence of a C<img>O structure may promote the adsorption and activation of acetylene molecules. In this study, a series of phenyl-based ligands containing X = O (X = C, N, S, and P) structures were used to prepare Pt-Lx/AC catalysts via the impregnation method. Performance evaluation revealed that the Pt-L5/AC catalyst, with 4-nitrosophenol (L5) as the ligand, exhibited the best catalytic performance. System characterization and theoretical calculations indicated that the N = O structure in the L5 ligand enhances the electronic structure of the catalyst’s active center, while the benzene ring further optimizes the catalytic reaction microenvironment. Theoretical results also show that H2PtCl6 molecules with 4-nitrosophenol ligands have significant advantages in acetylene hydrochlorination kinetics, likely due to the dispersion of the electron density of the Pt core by the L5 ligands. The addition of chlorine atoms to the C<img>C bond of C2H2 molecules releases a substantial amount of energy, making the reaction irreversible and more thermodynamically favorable, and by using HCL molecules to dynamically compensate the active domain of Pt-based catalyst, the performance of Pt-based catalyst can be improved.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"692 ","pages":"Article 120113"},"PeriodicalIF":4.7,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143136835","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}

引用次数: 0

Hierarchization of a large chabazite crystal shaped with hydrogen difluoride and its catalytic performance in the MTO reaction

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-01-09 DOI: 10.1016/j.apcata.2025.120116

José Henrique Marques, Elen Maria Feliciano Pereira, Leandro Martins

Fully microporous SSZ-13 zeolites with CHA structure efficiently convert methanol to olefins (MTO) with high selectivity. Unfortunately, the microporosity that enables high selectivity is the same causing diffusion limitations for reactants and products. Modifying zeolite textures by post-synthetic treatment is an interesting strategy to overcome this issue. Herein, we synthesized a large acidic SSZ-13 zeolite crystal and then created a secondary porosity by treating it with an NH₄HF₂ solution. The strategy of using large crystals allowed for tracking the chemical and spatial coke evolution and the performance of catalysts in the MTO reaction. The NH₄HF₂ solution removed Si and Al atoms from the zeolite structure, mostly aluminum, creating mesopores. The formation of mesopores was accompanied by micropore degradation. The hierarchical zeolite performed better in the MTO reaction than the untreated zeolite. The tracking of coke during the reaction time revealed that the mesopores gave the catalyst a significantly higher lifetime despite coke growing into bulkier polyaromatic molecules with up to 4 aromatic rings. The spatial disposition of coke revealed by fluorescence confocal microscopy showed that the mesopores improve the utilization of the catalyst.

{"title":"Hierarchization of a large chabazite crystal shaped with hydrogen difluoride and its catalytic performance in the MTO reaction","authors":"José Henrique Marques, Elen Maria Feliciano Pereira, Leandro Martins","doi":"10.1016/j.apcata.2025.120116","DOIUrl":"10.1016/j.apcata.2025.120116","url":null,"abstract":"<div><div>Fully microporous SSZ-13 zeolites with CHA structure efficiently convert methanol to olefins (MTO) with high selectivity. Unfortunately, the microporosity that enables high selectivity is the same causing diffusion limitations for reactants and products. Modifying zeolite textures by post-synthetic treatment is an interesting strategy to overcome this issue. Herein, we synthesized a large acidic SSZ-13 zeolite crystal and then created a secondary porosity by treating it with an NH4HF2 solution. The strategy of using large crystals allowed for tracking the chemical and spatial coke evolution and the performance of catalysts in the MTO reaction. The NH4HF2 solution removed Si and Al atoms from the zeolite structure, mostly aluminum, creating mesopores. The formation of mesopores was accompanied by micropore degradation. The hierarchical zeolite performed better in the MTO reaction than the untreated zeolite. The tracking of coke during the reaction time revealed that the mesopores gave the catalyst a significantly higher lifetime despite coke growing into bulkier polyaromatic molecules with up to 4 aromatic rings. The spatial disposition of coke revealed by fluorescence confocal microscopy showed that the mesopores improve the utilization of the catalyst.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"692 ","pages":"Article 120116"},"PeriodicalIF":4.7,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143136828","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}

引用次数: 0

Long-term stability of Au nanoparticles on rutile-like Ti1-xFexO2 solid solutions for low-temperature CO oxidation

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-01-09 DOI: 10.1016/j.apcata.2025.120108

Franklin J. Méndez , Alejandro Herrera-González , Antonio Morales , Carlos Ángeles-Chávez , Amado F. García-Ruiz , Elim Albiter , Dora A. Solís-Casados , Xim Bokhimi

Rutile and Fe-doped rutile were synthesized at low temperatures to support Au NPs. Selected samples were characterized using XRD, SEM-EDS, HRTEM, STEM-HAADF, H₂-TPR, XPS, FTIR and DRIFT spectroscopy of adsorbed CO molecules. To enrich the interpretation, we performed DFT calculation on clusters of rutile, Fe-doped rutile and metallic gold interacting with CO molecules. Catalysts were tested in the CO oxidation reaction, focusing on the roles of activation-reaction time, Au loading, Fe-modification, and long-term aging on performance. Au-based Fe-doped rutile exhibited superior activity compared to the unmodified rutile catalyst. Long-term aging resulted in catalyst deactivation, but reactivation under hydrogen restored the high activity levels. Fe incorporation into rutile promoted the stabilization of the Au NPs by increasing the number of oxygen atoms on the surface, which act as pinning centers. This stabilization prevented the mobility and growth of the Au NPs, improving their dispersion.

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