Journal of Catalysis最新文献

英文中文

Engineering two-dimensional multilayer heterostructure of internal electric field to enhance CO2 photoreduction

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-03-02 DOI: 10.1016/j.jcat.2025.116053

Jia Li , Yang Li , Yingshan Zeng , Yang Liu , Zhengguo Song , Zhi Liu

CO₂ photo reduction provides a feasible technique to solve climate issues and promote carbon neutrality. However, the efficiency of CO₂ photo reduction is severely depressed by the rapid recombination of photo generated carriers within photo catalysts, restricting the participation of electrons in the reduction process. In this study, we successfully construct a two-dimensional (2D) multilayer internal electric field (IEF) heterostructure by engineering the interface between NiAl-LDH and ZnV₂O₆ (ZNA). Driven by the IEF, the separation of photo generated electron-hole pairs is significantly enhanced, leading to the increased utilization efficiency of carriers for active sites. The best-performing sample of ZNA-2 achieves a highest CO yield of 695.8 μmol g⁻¹, approximately 30.5-fold higher than that of pristine ZnV₂O₆. Photo electrochemical measurement and density functional theory (DFT) calculation results reveal that the 2D-2D stacked structure generates multiple interlayer built-in electric fields, which are crucial for enhancing carrier separation and suppressing recombination. Adsorption energy and intermediate COOH* analysis reveal that ZNA-2 significantly lowers the adsorption energy of CO₂, promoting its stable adsorption and subsequent conversion. Moreover, the unique 2D multilayer IEF heterostructure greatly facilitates the formation of key intermediate COOH* and the desorption of CO during CO₂ photo reduction, leading to high CO activity and selectivity. The present work discloses the unprecedented potential of 2D multilayer IEF heterostructures for efficient CO₂ photo reduction, marking a significant advancement over conventional 2D counterparts.

{"title":"Engineering two-dimensional multilayer heterostructure of internal electric field to enhance CO2 photoreduction","authors":"Jia Li , Yang Li , Yingshan Zeng , Yang Liu , Zhengguo Song , Zhi Liu","doi":"10.1016/j.jcat.2025.116053","DOIUrl":"10.1016/j.jcat.2025.116053","url":null,"abstract":"<div><div>CO<sub>2</sub> photo reduction provides a feasible technique to solve climate issues and promote carbon neutrality. However, the efficiency of CO<sub>2</sub> photo reduction is severely depressed by the rapid recombination of photo generated carriers within photo catalysts, restricting the participation of electrons in the reduction process. In this study, we successfully construct a two-dimensional (2D) multilayer internal electric field (IEF) heterostructure by engineering the interface between NiAl-LDH and ZnV<sub>2</sub>O<sub>6</sub> (ZNA). Driven by the IEF, the separation of photo generated electron-hole pairs is significantly enhanced, leading to the increased utilization efficiency of carriers for active sites. The best-performing sample of ZNA-2 achieves a highest CO yield of 695.8 μmol g<sup>−1</sup>, approximately 30.5-fold higher than that of pristine ZnV<sub>2</sub>O<sub>6</sub>. Photo electrochemical measurement and density functional theory (DFT) calculation results reveal that the 2D-2D stacked structure generates multiple interlayer built-in electric fields, which are crucial for enhancing carrier separation and suppressing recombination. Adsorption energy and intermediate COOH* analysis reveal that ZNA-2 significantly lowers the adsorption energy of CO<sub>2</sub>, promoting its stable adsorption and subsequent conversion. Moreover, the unique 2D multilayer IEF heterostructure greatly facilitates the formation of key intermediate COOH* and the desorption of CO during CO<sub>2</sub> photo reduction, leading to high CO activity and selectivity. The present work discloses the unprecedented potential of 2D multilayer IEF heterostructures for efficient CO<sub>2</sub> photo reduction, marking a significant advancement over conventional 2D counterparts.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"445 ","pages":"Article 116053"},"PeriodicalIF":6.5,"publicationDate":"2025-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143532602","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}

引用次数: 0

Nickel-catalyzed CN bond formation of diarylamine between nitroarenes and aryl Grignard reagents

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-02-28 DOI: 10.1016/j.jcat.2025.116050

Wangjun Guo , Jianqun Liu , Hongli Liu , Yadong Liu , Zhisheng Wu , Minchang Wang , Yi Niu

In recent years, transition-metal-catalyzed CN bond formation from nitroarenes and aryl Grignard reagents has emerged as a promising and highly efficient method. Despite this, dinitro aromatic compounds have received limited attention in this context. Herein, we disclose a novel approach for synthesizing diarylamines via Ni-catalyzed cross-coupling of Grignard reagents with both mono- and di-nitro aromatic compounds. This method demonstrates remarkable tolerance towards a wide range of functional groups, including COOEt, F, Cl, CN, CF₃, OCF₃, SCH₃, and pyridyl groups, allowing for the synthesis of various aminated arenes in moderate to good yields. This CN bond formation method offers a general and step-economical pathway to diaryl and polyaryl amines, paving the way for new synthetic possibilities.

引用次数: 0

Effectiveness factor for catalyst pellets of non-basic shapes 非基本形状催化剂颗粒的有效系数

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-02-28 DOI: 10.1016/j.jcat.2025.116052

Hong Yong Sohn , Bahador Abolpour

The shape of a catalyst pellet affects the overall rate of reaction when the reaction is influenced by mass and heat transfer processes. While traditional modeling approaches often assume simple, basic pellet shapes (such as spheres or cylinders), this work focused on the numerical modeling of catalyst pellets with non-basic geometries, which are commonly used in industry. Using numerical techniques, the effectiveness factors of catalyst pellets with various non-basic shapes as functions of the Thiele modulus were investigated. Results indicate that the effectiveness factors of catalyst pellets of non-basic shapes, such as a hollow cylinder, cone, parallelepiped and finite cylinder with hemispherical caps, may be given by a single relationship with a generalized Thiele modulus λ_p, much as for the cases of basic shapes of a sphere, a long cylinder and a flat slab. This definition of the generalized modulus further provides unified numerical criteria for negligible effects of pore diffusion as λ_p ≤ 0.3 where

E \approx 1

within ∼10 % error (or λ_p ≤ 0.1 if an accuracy within ∼1 % is required) and for reaching large λ_p asymptotic condition as λ_p ≥ 3 where

E \approx \frac{1}{λ_{p}}

within ∼10 % error (or λ_p ≥ 10 if an accuracy within ∼1 % is required). Finally, for any shape of the catalyst pellets, the effectiveness factor can be expressed by the following single equation:

E = \frac{1}{\sqrt{1 + λ_{p}^{2}}}

{"title":"Effectiveness factor for catalyst pellets of non-basic shapes","authors":"Hong Yong Sohn , Bahador Abolpour","doi":"10.1016/j.jcat.2025.116052","DOIUrl":"10.1016/j.jcat.2025.116052","url":null,"abstract":"<div><div>The shape of a catalyst pellet affects the overall rate of reaction when the reaction is influenced by mass and heat transfer processes. While traditional modeling approaches often assume simple, basic pellet shapes (such as spheres or cylinders), this work focused on the numerical modeling of catalyst pellets with non-basic geometries, which are commonly used in industry. Using numerical techniques, the effectiveness factors of catalyst pellets with various non-basic shapes as functions of the Thiele modulus were investigated. Results indicate that the effectiveness factors of catalyst pellets of non-basic shapes, such as a hollow cylinder, cone, parallelepiped and finite cylinder with hemispherical caps, may be given by a single relationship with a generalized Thiele modulus <em>λ<sub>p</sub></em>, much as for the cases of basic shapes of a sphere, a long cylinder and a flat slab. This definition of the generalized modulus further provides unified numerical criteria for negligible effects of pore diffusion as <em>λ<sub>p</sub></em> ≤ 0.3 where <span><math><mrow><mi>E</mi><mo>≈</mo><mn>1</mn></mrow></math></span> within ∼10 % error (or <em>λ<sub>p</sub></em> ≤ 0.1 if an accuracy within ∼1 % is required) and for reaching large <em>λ<sub>p</sub></em> asymptotic condition as <em>λ<sub>p</sub></em> ≥ 3 where <span><math><mrow><mi>E</mi><mo>≈</mo><mfrac><mn>1</mn><msub><mi>λ</mi><mi>p</mi></msub></mfrac></mrow></math></span> within ∼10 % error (or <em>λ<sub>p</sub></em> ≥ 10 if an accuracy within ∼1 % is required). Finally, for any shape of the catalyst pellets, the effectiveness factor can be expressed by the following single equation:</div><div><span><math><mrow><mi>E</mi><mo>=</mo><mfrac><mn>1</mn><msqrt><mrow><mn>1</mn><mo>+</mo><msubsup><mi>λ</mi><mrow><mi>p</mi></mrow><mn>2</mn></msubsup></mrow></msqrt></mfrac></mrow></math></span></div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"445 ","pages":"Article 116052"},"PeriodicalIF":6.5,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143526332","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}

引用次数: 0

Removal of carbon deposits on χ-Fe5C2 Fischer–Tropsch catalysts

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-02-27 DOI: 10.1016/j.jcat.2025.116030

Shiyue Li , Robert Pestman , A. Iulian Dugulan , Zhuowu Men , Peng Wang , Emiel J.M. Hensen

The removal of carbon deposits from carburized Fe-based Fischer–Tropsch catalysts is a critical aspect of their performance. In this study, a method is presented to remove carbon deposits from freshly prepared χ-Fe₅C₂. The method involves successive passivation and reduction steps, which do not affect the bulk structure of the χ-Fe₅C₂ catalyst. The passivation step transforms the carbonaceous deposits from a graphitic structure to a disordered oxygen-functionalized structure, facilitating its removal by a reduction step in hydrogen. This results in a higher initial activity of the catalyst and substantially shortens the induction period observed without such pretreatment. The findings underscore the possibility of improving catalytic performance of Fe-carbides by changing the structure and reactivity of carbonaceous deposits.

引用次数: 0

One object (MOFs catalyst and light) with multiple purposes: The photocatalytic precursor detoxification and photo-induced green synthesis for fabrication of eco-friendly filtrate reducer

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-02-27 DOI: 10.1016/j.jcat.2025.116049

Qiang Li , Ying Chen , Jian Luo , Xiaobing Lu , Xiao Luo , Jingpeng Cai , Peipei Wang , Wuli Han , Yufan Lan

With the increasingly stringent environmental rules around the world, new drilling fluid additives having high efficiency, non-biotoxicity and low cost by green synthesis strategy will be the developing trends. Herein, under acting on the prefabricated MIL-Fe/NH₂-D(5) photocatalyst, the photo-induced detoxification of toxic sulfonated phenolic resin (SMP-3) was successfully completed for the first time, which further photopolymerized with tea polyphenol (TP), acrylamide (AM) and 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) to prepare eco-friendly fluid loss agent LI-3. The homemade MIL-Fe/NH₂-D(5) demonstrates dramatically increased light absorption in UV–VIS-NIR range with a significantly reduced band gap of 1.68 eV, and exhibits excellent efficiency of separating interface charges with rapid transfer dynamic. As expected, LI-3 filtrate reducer effectively controls the rheology of slurry, and possesses excellent loss-reducing properties even at high temperatures and high salinity conditions. Compared with base mud, the filtrate volumes of LI-3/BT-WBDFs containing 2.0 % LI-3 are reduced by 83.91 % and 83.42 % before and after aging at 180 °C, respectively. Finally, the possible mechanisms involved are explored. Particularly in both photo-induced detoxification and green synthesis periods, the photo thermal conversion based on localized surface plasmon resonance (LSPR) ensures mild conditions with energy saving.

{"title":"One object (MOFs catalyst and light) with multiple purposes: The photocatalytic precursor detoxification and photo-induced green synthesis for fabrication of eco-friendly filtrate reducer","authors":"Qiang Li , Ying Chen , Jian Luo , Xiaobing Lu , Xiao Luo , Jingpeng Cai , Peipei Wang , Wuli Han , Yufan Lan","doi":"10.1016/j.jcat.2025.116049","DOIUrl":"10.1016/j.jcat.2025.116049","url":null,"abstract":"<div><div>With the increasingly stringent environmental rules around the world, new drilling fluid additives having high efficiency, non-biotoxicity and low cost by green synthesis strategy will be the developing trends. Herein, under acting on the prefabricated MIL-Fe/NH<sub>2</sub>-D(5) photocatalyst, the photo-induced detoxification of toxic sulfonated phenolic resin (SMP-3) was successfully completed for the first time, which further photopolymerized with tea polyphenol (TP), acrylamide (AM) and 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) to prepare eco-friendly fluid loss agent LI-3. The homemade MIL-Fe/NH<sub>2</sub>-D(5) demonstrates dramatically increased light absorption in UV–VIS-NIR range with a significantly reduced band gap of 1.68 eV, and exhibits excellent efficiency of separating interface charges with rapid transfer dynamic. As expected, LI-3 filtrate reducer effectively controls the rheology of slurry, and possesses excellent loss-reducing properties even at high temperatures and high salinity conditions. Compared with base mud, the filtrate volumes of LI-3/BT-WBDFs containing 2.0 % LI-3 are reduced by 83.91 % and 83.42 % before and after aging at 180 °C, respectively. Finally, the possible mechanisms involved are explored. Particularly in both photo-induced detoxification and green synthesis periods, the photo thermal conversion based on localized surface plasmon resonance (LSPR) ensures mild conditions with energy saving.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"446 ","pages":"Article 116049"},"PeriodicalIF":6.5,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143507459","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}

引用次数: 0

Kinetics of hydrogen release from ammonia borane and role of the support for supported Ru catalysts in methanol solvent

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-02-25 DOI: 10.1016/j.jcat.2025.116041

Adam T. Twombly, James W. Harris

Ruthenium catalysts are promising for the catalytic release of H₂ from ammonia borane (AB). The reaction kinetics and the role of the support in the release of H₂ from AB in methanol solvent were studied using a series of Ru nanoparticle catalysts on various supports (SiO₂, carbon, γ-Al₂O₃, and TiO₂). Catalysts were synthesized using incipient wetness impregnation and solution deposition (SD) methods and characterized using N₂ physisorption, X-ray diffraction, inductively coupled plasma-optical emission spectroscopy, CO diffuse reflectance infrared Fourier transform spectroscopy, and transmission electron microscopy. The reaction kinetics were examined by measuring initial rates using a semi-batch reactor with a constant flow through the headspace analyzed by online mass spectrometry. The Ru/TiO₂-SD and Ru/C catalysts had the highest measured initial rates compared to the Ru/SiO₂ and Ru/Al₂O₃. Measured apparent activation energies were relatively similar between all catalysts. Regression of initial rates as a function of AB concentration was done for two different rate equations derived from two different proposed mechanisms for AB methanolysis. Both mechanisms were able to sufficiently describe trends in H₂ formation rate versus concentration at low AB concentrations. However, determination of which of the two proposed mechanisms best captures the trends in the data trends was inconclusive due to the lack of a statistically significant difference between degree-of-fit of the two models. Stability tests showed that Ru/C was less prone to deactivation over repeated use compared to Ru supported on the oxides. This study presents a comprehensive examination of the kinetics of AB methanolysis on different supported Ru catalysts; analysis of reaction mechanisms on all catalysts revealed similar apparent first order rate constants from either proposed kinetic models. This study demonstrates that while the support has relatively little influence on the measured reaction rates, carbon may be a preferred support given the decreased deactivation observed relative to the other supports tested.

{"title":"Kinetics of hydrogen release from ammonia borane and role of the support for supported Ru catalysts in methanol solvent","authors":"Adam T. Twombly, James W. Harris","doi":"10.1016/j.jcat.2025.116041","DOIUrl":"10.1016/j.jcat.2025.116041","url":null,"abstract":"<div><div>Ruthenium catalysts are promising for the catalytic release of H<sub>2</sub> from ammonia borane (AB). The reaction kinetics and the role of the support in the release of H<sub>2</sub> from AB in methanol solvent were studied using a series of Ru nanoparticle catalysts on various supports (SiO<sub>2</sub>, carbon, γ-Al<sub>2</sub>O<sub>3</sub>, and TiO<sub>2</sub>). Catalysts were synthesized using incipient wetness impregnation and solution deposition (SD) methods and characterized using N<sub>2</sub> physisorption, X-ray diffraction, inductively coupled plasma-optical emission spectroscopy, CO diffuse reflectance infrared Fourier transform spectroscopy, and transmission electron microscopy. The reaction kinetics were examined by measuring initial rates using a semi-batch reactor with a constant flow through the headspace analyzed by online mass spectrometry. The Ru/TiO<sub>2</sub>-SD and Ru/C catalysts had the highest measured initial rates compared to the Ru/SiO<sub>2</sub> and Ru/Al<sub>2</sub>O<sub>3</sub>. Measured apparent activation energies were relatively similar between all catalysts. Regression of initial rates as a function of AB concentration was done for two different rate equations derived from two different proposed mechanisms for AB methanolysis. Both mechanisms were able to sufficiently describe trends in H<sub>2</sub> formation rate versus concentration at low AB concentrations. However, determination of which of the two proposed mechanisms best captures the trends in the data trends was inconclusive due to the lack of a statistically significant difference between degree-of-fit of the two models. Stability tests showed that Ru/C was less prone to deactivation over repeated use compared to Ru supported on the oxides. This study presents a comprehensive examination of the kinetics of AB methanolysis on different supported Ru catalysts; analysis of reaction mechanisms on all catalysts revealed similar apparent first order rate constants from either proposed kinetic models. This study demonstrates that while the support has relatively little influence on the measured reaction rates, carbon may be a preferred support given the decreased deactivation observed relative to the other supports tested.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"445 ","pages":"Article 116041"},"PeriodicalIF":6.5,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486066","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}

引用次数: 0

Palladium-NHC mediated telomerization of aromatic alcohols

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-02-25 DOI: 10.1016/j.jcat.2025.116048

Lorenzo Palio , Lucas Piglialepre , Tiphaine Richard , Clément Dumont , Isabelle Suisse , Catherine S.J. Cazin , Steven P. Nolan , Mathieu Sauthier

The telomerization reaction of dienes with alcohols mediated by organopalladium complexes represents a versatile method to convert butadiene into value-added chemicals. The use of aromatic alcohols in the telomerization is still an under-explored area that has attracted increased interest in recent years. In this contribution, we examine the catalytic behaviour of a series of well-defined palladium N-heterocyclic carbene precatalysts (Pd-NHC) in the telomerization of butadiene with aromatic alcohols. The process was optimized by studying the influence of Pd/L ratio, of the base and of the pre-catalyst structure. The versatility of the method was tested employing a series of aromatic alcohols, including lignin-type phenols. In the context of biomass valorisation, an explorative study on the telomerization with lignin was carried out.

引用次数: 0

CuPt dual-atom synergistic catalyst boost carbon-oxygen bonds hydrogenation

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-02-24 DOI: 10.1016/j.jcat.2025.116047

Ziheng Zhen , Antai Li , Tiantian Xiao , Maoshuai Li , Jing Lv , Shouying Huang , Yue Wang , Xinbin Ma

Bimetallic catalyst with dual-atom pairs has drawn much attention in heterogeneous catalysis due to their unique synergistic effects. In this work, we prepared a series CeO₂ supported Cu-Pt dual sites catalysts and found the optimized one of 2Cu0.025Pt/CeO₂ exhibited excellent performance in the hydrogenation of methyl acetate (MA). Its product yield of ethanol was as 4 times as that of 2Cu/CeO₂ catalyst under the same reaction conditions, with only 0.025 wt% Pt addition. Combined with various characterizations and contrast samples, it is demonstrated that the post-deposited trace Pt species preferentially located besides the copper atoms and formed Cu-Pt atomic pairs. But when further increasing the loading of Pt, the aggregation of Cu happened, leading to a rapid decrease of activity. To reveal the role of Cu-Pt atom pairs in the hydrogenation of carbon–oxygen bonds reactions, we conducted chemisorption experiments and DFT simulations. It is suggested that Cu-Pt atomic pairs significantly enhanced the adsorption and activation capability of both the MA and H₂ molecules during the reaction. These insights may provide synthesis and design strategy for high-performance dual-atom sites catalysts for the carbon–oxygen bonds hydrogenation reactions.

{"title":"CuPt dual-atom synergistic catalyst boost carbon-oxygen bonds hydrogenation","authors":"Ziheng Zhen , Antai Li , Tiantian Xiao , Maoshuai Li , Jing Lv , Shouying Huang , Yue Wang , Xinbin Ma","doi":"10.1016/j.jcat.2025.116047","DOIUrl":"10.1016/j.jcat.2025.116047","url":null,"abstract":"<div><div>Bimetallic catalyst with dual-atom pairs has drawn much attention in heterogeneous catalysis due to their unique synergistic effects. In this work, we prepared a series CeO<sub>2</sub> supported Cu-Pt dual sites catalysts and found the optimized one of 2Cu0.025Pt/CeO<sub>2</sub> exhibited excellent performance in the hydrogenation of methyl acetate (MA). Its product yield of ethanol was as 4 times as that of 2Cu/CeO<sub>2</sub> catalyst under the same reaction conditions, with only 0.025 wt% Pt addition. Combined with various characterizations and contrast samples, it is demonstrated that the post-deposited trace Pt species preferentially located besides the copper atoms and formed Cu-Pt atomic pairs. But when further increasing the loading of Pt, the aggregation of Cu happened, leading to a rapid decrease of activity. To reveal the role of Cu-Pt atom pairs in the hydrogenation of carbon–oxygen bonds reactions, we conducted chemisorption experiments and DFT simulations. It is suggested that Cu-Pt atomic pairs significantly enhanced the adsorption and activation capability of both the MA and H<sub>2</sub> molecules during the reaction. These insights may provide synthesis and design strategy for high-performance dual-atom sites catalysts for the carbon–oxygen bonds hydrogenation reactions.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"445 ","pages":"Article 116047"},"PeriodicalIF":6.5,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143477550","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}

引用次数: 0

Direct synthesis of amides from nitroarenes and carboxylic acids via CO-mediated reduction

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-02-22 DOI: 10.1016/j.jcat.2025.116042

Mikhail A. Losev , Oleg I. Afanasyev , Denis Chusov

A highly efficient direct carbon monoxide-mediated protocol for converting nitroarenes and carboxylic acids to amides was developed. Investigation of the reaction kinetics and a Hammett study allowed us to reveal the reaction mechanism and the best reaction conditions. An observed apparent partial reaction order by nitroarene in this reaction is 0.5 indicating the switch of the rate-determining step during the course of the reaction. A highly valuable Vorinostat precursor with 99% purity was synthesized in a quantitative yield without any purification; the E-factor of the process was 0.35, which fits to the multiton chemistry reactions. All substrate scope was prepared using the simple Ru₃(CO)₁₂ as a catalyst, and TON up to 44,400 was achieved.

我们开发了一种一氧化碳介导的将硝基烯烃和羧酸转化为酰胺的高效直接方案。通过对反应动力学的研究和 Hammett 研究，我们揭示了反应机理和最佳反应条件。在该反应中，观察到硝基烯烃的明显部分反应顺序为 0.5，这表明在反应过程中决定速率的步骤发生了转换。在不进行任何纯化的情况下，我们定量合成了纯度为 99% 的高价值伏立诺司他前体；该过程的 E 因子为 0.35，符合多子化学反应。以简单的 Ru3(CO)12 为催化剂制备了所有底物范围，并实现了高达 44,400 吨的吨位。

引用次数: 0

Exhaustive reduction of aromatic esters and carboxylic acids with a homogeneous cobalt catalyst

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-02-21 DOI: 10.1016/j.jcat.2025.116034

Zi-Heng Zhang , Rui Sun , Yuan-Yuan Jiang , Jin-Qing Lin , Yan-Qiang Zhang , Bao-Hua Xu

A one-step procedure to exhaustively reduce aromatic esters and carboxylic acids to their corresponding tolyl derivatives is a significant transformation in organic synthesis, which remains challenging in homogeneous catalysis. In this study, it’s achieved by using the well-defined phosphinesulfonate chelated cobalt-based catalyst (Co(dppbsa)), along with NaBAr^F₄ as the basic additive and (MeO)₂MeSiH as the reductant. Particularly, this cobalt catalysis proceeds through ether intermediates. Experimental combined theoretical results support it follows an outer-sphere ionic hydrosilylation mechanism and the in situ formed cationic siloxane species are involved in the rate-limiting hydride transfer. The same system also enables the catalytic deoxygenation of aliphatic esters, aliphatic acids, and amides but terminating at the corresponding ethers, alkanols and secondary amines, respectively. These findings open up novel avenues for the catalytic application of phosphinesulfonate chelated complexes, potentially serving as the foundation for the exhaustive reduction of carboxylic skeletons with cobalt.

{"title":"Exhaustive reduction of aromatic esters and carboxylic acids with a homogeneous cobalt catalyst","authors":"Zi-Heng Zhang , Rui Sun , Yuan-Yuan Jiang , Jin-Qing Lin , Yan-Qiang Zhang , Bao-Hua Xu","doi":"10.1016/j.jcat.2025.116034","DOIUrl":"10.1016/j.jcat.2025.116034","url":null,"abstract":"<div><div>A one-step procedure to exhaustively reduce aromatic esters and carboxylic acids to their corresponding tolyl derivatives is a significant transformation in organic synthesis, which remains challenging in homogeneous catalysis. In this study, it’s achieved by using the well-defined phosphinesulfonate chelated cobalt-based catalyst (Co(dppbsa)), along with NaBAr<sup>F</sup><sub>4</sub> as the basic additive and (MeO)<sub>2</sub>MeSiH as the reductant. Particularly, this cobalt catalysis proceeds through ether intermediates. Experimental combined theoretical results support it follows an outer-sphere ionic hydrosilylation mechanism and the in situ formed cationic siloxane species are involved in the rate-limiting hydride transfer. The same system also enables the catalytic deoxygenation of aliphatic esters, aliphatic acids, and amides but terminating at the corresponding ethers, alkanols and secondary amines, respectively. These findings open up novel avenues for the catalytic application of phosphinesulfonate chelated complexes, potentially serving as the foundation for the exhaustive reduction of carboxylic skeletons with cobalt.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"445 ","pages":"Article 116034"},"PeriodicalIF":6.5,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462321","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}

引用次数: 0

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全部 ACS Publications Elsevier ieeexplore Springer The Royal Society of Chemistry Wiley

期刊

Journal of Catalysis

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