Journal of Catalysis最新文献

英文中文

The sandwich-shaped double S-scheme heterojuction OCN/BiOCl/Bi24O31Cl10 efficiently degrades levofloxacin and its charge transfer mechanism

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-03-04 DOI: 10.1016/j.jcat.2025.116055

Yuan Wei , Chao Liu , Tian-Tian Wang , Hong-Yu Wang , Yu-Miao Yang , Gao-Feng Shi , Guo-Ying Wang

The rapid recombination rate of photogenerated charges presents considerable challenges for the rational design of high-performance, stable photocatalysts. In this study, we integrated the characteristics of oxygen doping and heterojunctions into oxygen-doped g-C₃N₄/BiOCl/Bi₂₄O₃₁Cl₁₀ (OCN/BiOCl/Bi₂₄O₃₁Cl₁₀) using a straightforward impregnation-calcination method. Oxygen doping disrupts the symmetric atomic arrangement in pure-phase samples, optimizing the electronic configuration of active sites at the reaction interface and enhancing the coupling between anions and cations. The introduction of BiOCl, which offers an excellent coordination environment, in conjunction with Bi₂₄O₃₁Cl₁₀, creates a dual-S heterojunction. This structure establishes dual reaction interfaces that facilitate efficient dual electron ’transport channels,’ promoting the rapid transfer of charge carriers among OCN, BiOCl, and Bi₂₄O₃₁Cl₁₀. Experimental results demonstrate that the OCN/BiOCl/Bi₂₄O₃₁Cl₁₀ heterojunction material achieves a degradation efficiency of 96.1 % for 10 mg·L⁻¹ levofloxacin under visible light. Notably, in situ measurements obtained through Kelvin probe force microscopy (KPFM) and density functional theory (DFT) calculations jointly reveal a unique chemical environment and electronic structure arising from the formation of an internal electric field among OCN, BiOCl, and Bi₂₄O₃₁Cl₁₀, thereby providing enhanced pathways for the migration of photogenerated charge carriers. Furthermore, the heterostructure significantly reduces the transport distance of photogenically induced charges and decreases internal transport resistance, thereby improving the separation efficiency of photogenerated electron-hole pairs. This mechanism is crucial for the markedly enhanced photocatalytic degradation performance of OCN, BiOCl, and Bi₂₄O₃₁Cl₁₀ materials. In summary, this work explores the synergistic effects among multiple modifications, providing insights for the precise design of efficient and stable photocatalytic degradation systems.

{"title":"The sandwich-shaped double S-scheme heterojuction OCN/BiOCl/Bi24O31Cl10 efficiently degrades levofloxacin and its charge transfer mechanism","authors":"Yuan Wei , Chao Liu , Tian-Tian Wang , Hong-Yu Wang , Yu-Miao Yang , Gao-Feng Shi , Guo-Ying Wang","doi":"10.1016/j.jcat.2025.116055","DOIUrl":"10.1016/j.jcat.2025.116055","url":null,"abstract":"<div><div>The rapid recombination rate of photogenerated charges presents considerable challenges for the rational design of high-performance, stable photocatalysts. In this study, we integrated the characteristics of oxygen doping and heterojunctions into oxygen-doped g-C3N4/BiOCl/Bi24O31Cl10 (OCN/BiOCl/Bi24O31Cl10) using a straightforward impregnation-calcination method. Oxygen doping disrupts the symmetric atomic arrangement in pure-phase samples, optimizing the electronic configuration of active sites at the reaction interface and enhancing the coupling between anions and cations. The introduction of BiOCl, which offers an excellent coordination environment, in conjunction with Bi24O31Cl10, creates a dual-S heterojunction. This structure establishes dual reaction interfaces that facilitate efficient dual electron ’transport channels,’ promoting the rapid transfer of charge carriers among OCN, BiOCl, and Bi24O31Cl10. Experimental results demonstrate that the OCN/BiOCl/Bi24O31Cl10 heterojunction material achieves a degradation efficiency of 96.1 % for 10 mg·L−1 levofloxacin under visible light. Notably, in situ measurements obtained through Kelvin probe force microscopy (KPFM) and density functional theory (DFT) calculations jointly reveal a unique chemical environment and electronic structure arising from the formation of an internal electric field among OCN, BiOCl, and Bi24O31Cl10, thereby providing enhanced pathways for the migration of photogenerated charge carriers. Furthermore, the heterostructure significantly reduces the transport distance of photogenically induced charges and decreases internal transport resistance, thereby improving the separation efficiency of photogenerated electron-hole pairs. This mechanism is crucial for the markedly enhanced photocatalytic degradation performance of OCN, BiOCl, and Bi24O31Cl10 materials. In summary, this work explores the synergistic effects among multiple modifications, providing insights for the precise design of efficient and stable photocatalytic degradation systems.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"446 ","pages":"Article 116055"},"PeriodicalIF":6.5,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143538347","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

Effect of water impurities on promoted and unpromoted cobalt-catalysts during the ammonia decomposition reaction

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-03-03 DOI: 10.1016/j.jcat.2025.116054

Zahra Almisbaa , Philippe Sautet

The feedstock of the ammonia decomposition reaction often contains water impurities. Water-induced Co oxidation leads to catalyst deactivation. DFT-based microkinetic simulations of ammonia decomposition and water dissociation reactions are used to understand oxygen poisoning on promoted and unpromoted Co surfaces. Simulations show that catalyst oxidation only occurs at low NH₃ conversion and, at higher conversion, the produced H₂ reduces the catalyst. Hence, in a typical flow reactor, catalyst oxidation is likely to occur only at the reactor inlet. However, the oxidized zone can slowly propagate along the reactor and impact the catalyst stability. The adsorption of oxygen was stronger on BaO-promoted Co in comparison to pristine Co. However, Co-BaO is more sensitive to H₂ pressure and needs a lower ammonia conversion to prevent oxygen poisoning on the surface. This indicates that the BaO promoter plays a role in making the catalyst more resistant to O-induced poisoning during the ammonia decomposition reaction.

引用次数: 0

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>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.</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 λp, 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 λp ≤ 0.3 where <math><mrow><mi>E</mi><mo>≈</mo><mn>1</mn></mrow></math> within ∼10 % error (or λp ≤ 0.1 if an accuracy within ∼1 % is required) and for reaching large λp asymptotic condition as λp ≥ 3 where <math><mrow><mi>E</mi><mo>≈</mo><mfrac><mn>1</mn><msub><mi>λ</mi><mi>p</mi></msub></mfrac></mrow></math> within ∼10 % error (or λp ≥ 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><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></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/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.</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 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.</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 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.</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

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Journal of Catalysis

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