Journal of Catalysis最新文献

英文中文

Highly para-selective alkylation of toluene by methyl mercaptan over silylated ZSM-5 zeolite 硅烷化 ZSM-5 沸石上甲基硫醇对甲苯的高副选择性烷基化反应

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2024-10-28 DOI: 10.1016/j.jcat.2024.115828

Abdelilah Bayout , Claudia Cammarano , Izabel Medeiros Costa , Gleb Veryasov , Alexander Sachse , Vasile Hulea

Friedel-Crafts alkylation of toluene with methyl mercaptan has been investigated in the presence of H-ZSM-5 and SiO₂/H-ZSM-5 catalysts. The silica layers have been built on H-ZSM-5 zeolite by chemical liquid deposition of tetraethyl orthosilicate. The passivation with silica of the external surface of H-ZSM-5 zeolite has been confirmed by FT-IR spectroscopy and mesitylene isomerization, used as a model reaction. All catalysts exhibited notable behavior in the alkylation of toluene to xylenes. Efficiencies higher than 98 % in alkylation for both toluene and methyl mercaptan were obtained at 375 °C. In terms of para-selectivity, outstanding performance was revealed by the silylated zeolites. Thus, over 12 % SiO₂/H-ZSM-5, at 375 °C and WHSV = 9.4 g_{toluene+CH3SH} g_cat^-1h⁻¹, the para-xylene selectivity was close to 100 %. The experimental apparent activation energy for the toluene alkylation with methyl mercaptan catalyzed by H-ZSM-5 was 80 kJ/mol.

在 H-ZSM-5 和 SiO2/H-ZSM-5 催化剂存在下，研究了甲苯与甲硫醇的 Friedel-Crafts 烷基化反应。H-ZSM-5 沸石上的二氧化硅层是通过正硅酸四乙酯的化学液相沉积而形成的。H-ZSM-5 沸石外表面的二氧化硅钝化已通过傅立叶变换红外光谱和用作模型反应的间苯异构化得到证实。在甲苯烷基化为二甲苯的过程中，所有催化剂都表现出了显著的性能。在 375 °C 时，甲苯和甲硫醇的烷基化效率均高于 98%。就副选择性而言，硅烷化沸石的性能十分突出。因此，在 375 ℃ 和 WHSV = 9.4 gtoluene+CH3SH gcat-1h-1 条件下，12 % SiO2/H-ZSM-5 的对二甲苯选择性接近 100%。H-ZSM-5 催化甲苯与甲硫醇发生烷基化反应的实验表观活化能为 80 kJ/mol。

{"title":"Highly para-selective alkylation of toluene by methyl mercaptan over silylated ZSM-5 zeolite","authors":"Abdelilah Bayout , Claudia Cammarano , Izabel Medeiros Costa , Gleb Veryasov , Alexander Sachse , Vasile Hulea","doi":"10.1016/j.jcat.2024.115828","DOIUrl":"10.1016/j.jcat.2024.115828","url":null,"abstract":"<div><div>Friedel-Crafts alkylation of toluene with methyl mercaptan has been investigated in the presence of H-ZSM-5 and SiO<sub>2</sub>/H-ZSM-5 catalysts. The silica layers have been built on H-ZSM-5 zeolite by chemical liquid deposition of tetraethyl orthosilicate. The passivation with silica of the external surface of H-ZSM-5 zeolite has been confirmed by FT-IR spectroscopy and mesitylene isomerization, used as a model reaction. All catalysts exhibited notable behavior in the alkylation of toluene to xylenes. Efficiencies higher than 98 % in alkylation for both toluene and methyl mercaptan were obtained at 375 °C. In terms of <em>para</em>-selectivity, outstanding performance was revealed by the silylated zeolites. Thus, over 12 % SiO<sub>2</sub>/H-ZSM-5, at 375 °C and WHSV = 9.4 g<sub>toluene+CH3SH</sub> g<sub>cat</sub><sup>-1</sup>h<sup>−1</sup>, the <em>para</em>-xylene selectivity was close to 100 %. The experimental apparent activation energy for the toluene alkylation with methyl mercaptan catalyzed by H-ZSM-5 was 80 kJ/mol.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"440 ","pages":"Article 115828"},"PeriodicalIF":6.5,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142519375","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Deactivation of Cu/ZnO/Al2O3 catalysts by sintering in liquid phase assisted methanol synthesis from CO2/H2 and a way to counteract it Cu/ZnO/Al2O3 催化剂在液相辅助 CO2/H2 合成甲醇过程中的烧结失活问题及解决方法

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2024-10-28 DOI: 10.1016/j.jcat.2024.115829

Dominic Walter , Jonathan Hackebeil , Conrad Hübler , Erik Schumann , Andreas Lißner , Bianca Störr , Mykhaylo Motylenko , David Rafaja , Florian Mertens

The sintering process on Cu/ZnO/Al₂O₃ catalysts in the heterogeneous liquid phase assisted methanol synthesis from CO₂/H₂ was investigated. In order to better understand the sintering event, in addition to standard methods (XRD, XPS, BET, ICP-OES) microscopic techniques with different magnifications such as SEM-EDX, AFM, and TEM were used. Water has been identified as the sintering agent. In addition to eliminating water with CO, another way was found to remove water from the catalyst surface and therefore to counteract the sintering during catalysis. This goal can be achieved by using highly polar solvents allowing to synthesize MeOH solely from carbon dioxide and hydrogen, without deactivating the catalyst or using carbon monoxide.

研究了异相液相辅助 CO2/H2 合成甲醇过程中 Cu/ZnO/Al2O3 催化剂的烧结过程。为了更好地了解烧结过程，除了使用标准方法（XRD、XPS、BET、ICP-OES）外，还使用了不同放大倍数的显微技术，如 SEM-EDX、AFM 和 TEM。水已被确定为烧结剂。除了用一氧化碳消除水之外，我们还找到了另一种方法来去除催化剂表面的水，从而抵消催化过程中的烧结。这一目标可以通过使用高极性溶剂来实现，这样就可以在不使催化剂失活或不使用一氧化碳的情况下，仅用二氧化碳和氢气合成甲基氧化汞。

引用次数: 0

Kinetic analysis of the self-discharge of the NiOOH OER active phase in KOH electrolyte: insights from in-situ Raman and UV–Vis reflectance spectroscopies KOH 电解液中 NiOOH OER 活性相的自放电动力学分析：原位拉曼光谱和紫外可见反射光谱的启示

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2024-10-26 DOI: 10.1016/j.jcat.2024.115823

Harol Moreno Fernández , Achim Alkemper , Kai Wang , Crizaldo Jr. Mempin , Julia Gallenbeger , Jan P. Hofmann

NiOOH has been established as the active phase of NiO-based electrocatalysts in the alkaline Oxygen Evolution Reaction (OER). Here, we investigate the self-discharge behavior of NiOOH electrodes under open circuit potential (OCP) conditions in 1 M KOH electrolyte by monitoring phase changes via in-situ Raman and UV–Vis reflectance spectroscopies and performing kinetic analyses on the OCP and spectroscopic data. Our findings reveal a linear phase change from NiOOH to Ni(OH)₂ over time, indicative of a 0^th-order reduction reaction. Contrarily, the OCP evolution associated with this phase reduction displayed a combination of linear and exponential decay patterns as a result of various kinetics, including Faradaic processes and diffusion-controlled mechanisms, influencing the self-discharge potential over 1.25 V (vs RHE). An additional linear region at lower potentials (<1.25 V (vs RHE)) suggests that charge redistribution due to the phase change from α-Ni(OH)₂ to β-Ni(OH)₂ dominates the self-discharge, a behavior confirmed by in-situ UV–Vis reflectance spectroscopy. These findings highlight the effectiveness of combining in-situ Raman and UV–Vis spectroscopy with electrochemical data for real-time monitoring of electrochemical processes, here potential-dependent electrocatalyst phase changes, leading to a more detailed and accurate understanding of the dynamic behavior, phase change kinetics, and self-discharge behaviors of solid electrocatalysts that can guide the design of more efficient and durable energy storage and conversion materials.

在碱性氧进化反应（OER）中，NiOOH 已被确定为基于 NiO 的电催化剂的活性相。在此，我们通过原位拉曼光谱和紫外可见反射光谱监测相变，并对 OCP 和光谱数据进行动力学分析，研究了 NiOOH 电极在 1 M KOH 电解液中开路电位 (OCP) 条件下的自放电行为。我们的研究结果表明，随着时间的推移，从 NiOOH 到 Ni(OH)2 的相变呈线性变化，这表明发生了 0 阶还原反应。与此相反，与这种相还原相关的 OCP 演变显示出线性和指数衰减模式的结合，这是各种动力学（包括法拉第过程和扩散控制机制）的结果，影响了 1.25 V 以上的自放电电位（相对于 RHE）。在较低电位（<1.25 V (vs RHE)）下的额外线性区域表明，从 α-Ni(OH)2 到 β-Ni(OH) 2 的相变引起的电荷再分布主导了自放电，原位紫外可见反射光谱证实了这一行为。这些发现凸显了将原位拉曼光谱和紫外可见光谱与电化学数据相结合，实时监测电化学过程（这里指电势相关的电催化剂相变）的有效性，从而更详细、更准确地了解固体电催化剂的动态行为、相变动力学和自放电行为，为设计更高效、更耐用的储能和转换材料提供指导。

{"title":"Kinetic analysis of the self-discharge of the NiOOH OER active phase in KOH electrolyte: insights from in-situ Raman and UV–Vis reflectance spectroscopies","authors":"Harol Moreno Fernández , Achim Alkemper , Kai Wang , Crizaldo Jr. Mempin , Julia Gallenbeger , Jan P. Hofmann","doi":"10.1016/j.jcat.2024.115823","DOIUrl":"10.1016/j.jcat.2024.115823","url":null,"abstract":"<div><div>NiOOH has been established as the active phase of NiO-based electrocatalysts in the alkaline Oxygen Evolution Reaction (OER). Here, we investigate the self-discharge behavior of NiOOH electrodes under open circuit potential (OCP) conditions in 1 M KOH electrolyte by monitoring phase changes via in-situ Raman and UV–Vis reflectance spectroscopies and performing kinetic analyses on the OCP and spectroscopic data. Our findings reveal a linear phase change from NiOOH to Ni(OH)<sub>2</sub> over time, indicative of a 0<sup>th</sup>-order reduction reaction. Contrarily, the OCP evolution associated with this phase reduction displayed a combination of linear and exponential decay patterns as a result of various kinetics, including Faradaic processes and diffusion-controlled mechanisms, influencing the self-discharge potential over 1.25 V (vs RHE). An additional linear region at lower potentials (<1.25 V (vs RHE)) suggests that charge redistribution due to the phase change from α-Ni(OH)<sub>2</sub> to β-Ni(OH)<sub>2</sub> dominates the self-discharge, a behavior confirmed by in-situ UV–Vis reflectance spectroscopy. These findings highlight the effectiveness of combining in-situ Raman and UV–Vis spectroscopy with electrochemical data for real-time monitoring of electrochemical processes, here potential-dependent electrocatalyst phase changes, leading to a more detailed and accurate understanding of the dynamic behavior, phase change kinetics, and self-discharge behaviors of solid electrocatalysts that can guide the design of more efficient and durable energy storage and conversion materials.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"440 ","pages":"Article 115823"},"PeriodicalIF":6.5,"publicationDate":"2024-10-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142519377","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Efficient photoreforming of plastic waste using a high-entropy oxide catalyst 使用高熵氧化物催化剂对塑料废弃物进行高效光转化

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2024-10-24 DOI: 10.1016/j.jcat.2024.115808

Thanh Tam Nguyen , Kaveh Edalati

Simultaneous catalytic hydrogen (H₂) production and plastic waste degradation under light, known as photoreforming, is a novel approach to green fuel production and efficient waste management. Here, we use a high-entropy oxide (HEO), a new family of catalysts with five or more principal cations in their structure, for plastic degradation and simultaneous H₂ production. The HEO shows higher activity than that of P25 TiO₂, a benchmark photocatalyst, for the degradation of polyethylene terephthalate (PET) plastics in water. Several valuable products are produced by photoreforming of PET bottles and microplastics including H₂, terephthalate, ethylene glycol and formic acid. The high activity is attributed to the diverse existence of several cations in the HEO lattice, lattice defects, and appropriate charge carrier lifetime. These findings suggest that HEOs possess high potential as new catalysts for concurrent plastic waste conversion and clean H₂ production.

在光照下同时催化制氢（H2）和降解塑料废物（称为光转化）是一种新型的绿色燃料生产和高效废物管理方法。在这里，我们使用一种高熵氧化物（HEO）来降解塑料并生产氢气。HEO 是一种新型催化剂，其结构中含有五个或五个以上的主阳离子。在降解水中的聚对苯二甲酸乙二酯（PET）塑料方面，高熵氧化物的活性高于基准光催化剂 P25 TiO2。PET 瓶和微塑料的光转化可产生多种有价值的产品，包括 H2、对苯二甲酸酯、乙二醇和甲酸。高活性归因于 HEO 晶格中存在多种阳离子、晶格缺陷和适当的电荷载流子寿命。这些研究结果表明，作为新型催化剂，HEOs 在同时转化塑料废物和生产清洁的 H2 方面具有很高的潜力。

引用次数: 0

Enhancing coke resistance of Ni-based spinel-type oxides by tuning the configurational entropy 通过调整构型熵增强镍基尖晶石型氧化物的抗焦性

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2024-10-24 DOI: 10.1016/j.jcat.2024.115819

Shuangshuang Zhang , Ying Gao , Qiang Niu , Pengfei Zhang

The reforming of CH₄ and CO₂ into syngas is a highly relevant technology for energy conservation and reducing greenhouse gas emissions, attracting widespread attention in the industry. Inspired by this, this work proposes a general criterion for coke-resistant nickel-based catalysts. By leveraging the high-entropy effect and the lattice distortion of the structure, a high-entropy (NiCaMgZnCo)Al₁₀O_x catalyst was synthesized. The high-entropy oxide exhibited good activity and stability during the DRM reaction over 100 h at 800°C and 650°C, producing only a minimal amount of easily removable carbon deposition. O₂-TPO, CO₂-TPD, CH₄-TPSR, CO₂-TPSR, DFT and in situ DRIFT were employed to investigate the mechanism of carbon deposition elimination on the surface of the high-entropy catalyst. Then, a high-entropy strategy for designing coke-resistant catalysts was proposed. This strategy may soon inspire the development of catalysts with enhanced stability and anti-coke deposition properties for various catalytic applications.

将 CH4 和 CO2 转化为合成气是一项与节能和减少温室气体排放高度相关的技术，受到业界的广泛关注。受此启发，本研究提出了耐焦化镍基催化剂的一般标准。利用高熵效应和晶格畸变结构，合成了一种高熵 (NiCaMgZnCo)Al10Ox 催化剂。这种高熵氧化物在 800°C 和 650°C 温度下进行 DRM 反应 100 小时期间表现出良好的活性和稳定性，仅产生极少量的易去除碳沉积。采用 O2-TPO、CO2-TPD、CH4-TPSR、CO2-TPSR、DFT 和原位 DRIFT 等方法研究了高熵催化剂表面碳沉积消除的机理。然后，提出了一种设计抗焦催化剂的高熵策略。该策略可能很快会激励人们开发出具有更高的稳定性和抗焦炭沉积性能的催化剂，用于各种催化应用。

{"title":"Enhancing coke resistance of Ni-based spinel-type oxides by tuning the configurational entropy","authors":"Shuangshuang Zhang , Ying Gao , Qiang Niu , Pengfei Zhang","doi":"10.1016/j.jcat.2024.115819","DOIUrl":"10.1016/j.jcat.2024.115819","url":null,"abstract":"<div><div>The reforming of CH<sub>4</sub> and CO<sub>2</sub> into syngas is a highly relevant technology for energy conservation and reducing greenhouse gas emissions, attracting widespread attention in the industry. Inspired by this, this work proposes a general criterion for coke-resistant nickel-based catalysts. By leveraging the high-entropy effect and the lattice distortion of the structure, a high-entropy (NiCaMgZnCo)Al<sub>10</sub>O<sub>x</sub> catalyst was synthesized. The high-entropy oxide exhibited good activity and stability during the DRM reaction over 100 h at 800°C and 650°C, producing only a minimal amount of easily removable carbon deposition. O<sub>2</sub>-TPO, CO<sub>2</sub>-TPD, CH<sub>4</sub>-TPSR, CO<sub>2</sub>-TPSR, DFT and in situ DRIFT were employed to investigate the mechanism of carbon deposition elimination on the surface of the high-entropy catalyst. Then, a high-entropy strategy for designing coke-resistant catalysts was proposed. This strategy may soon inspire the development of catalysts with enhanced stability and anti-coke deposition properties for various catalytic applications.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"440 ","pages":"Article 115819"},"PeriodicalIF":6.5,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142488179","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

Propylene oligomerization over SiO2-overcoated oxides 二氧化硅包覆氧化物上的丙烯低聚反应

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2024-10-24 DOI: 10.1016/j.jcat.2024.115820

Andrew T.Y. Wolek , Evan Sowinski , Rajamani Gounder , Justin M. Notestein

Catalytic oligomerization of light olefins is an important CC coupling strategy that can be used to produce high-value transportation fuels and chemicals from shale gas and biomass feedstocks. In this work, vapor-phase propylene oligomerization was studied over a series of overcoated SiO₂-MOx materials, whose acid site densities and strengths are tunable by the amount of SiO₂ deposition and the nature of the core oxide. These materials contain acid sites only on particle external surfaces, limiting pore diffusion artifacts. SiO₂-MOx materials were prepared by depositing stoichiometric amounts of tetraethyl orthosilicate (TEOS) onto Al₂O₃, anatase TiO₂, Nb₂O₅, and ZrO₂. Compared to the unmodified oxides, which are poor propylene oligomerization catalysts, the SiO₂-MOx materials exhibit moderate activity with Al₂O₃, TiO₂, and Nb₂O₅ core materials performing better than commercial amorphous silica alumina (ASA) on a surface area basis. The activity of the materials appears to be primarily driven by their Brønsted acid strength as measured by ³¹P TMPO MAS NMR with the rates ranked in order SiO₂/Al₂O₃ > SiO₂/TiO₂ ≈ SiO₂/Nb₂O₅ > SiO₂/ZrO₂. This study shows that SiO₂-overcoated materials are a tunable class of materials that are active for vapor-phase propylene oligomerization.

轻烯烃的催化低聚是一种重要的 CC 耦合策略，可用于利用页岩气和生物质原料生产高价值的运输燃料和化学品。在这项工作中，研究了气相丙烯在一系列覆膜二氧化硅-氧化物材料上的低聚过程，这些材料的酸性位点密度和强度可通过二氧化硅沉积量和核心氧化物的性质进行调整。这些材料仅在颗粒外表面含有酸性位点，从而限制了孔隙扩散伪影。SiO2-MOx 材料是通过在 Al2O3、锐钛型 TiO2、Nb2O5 和 ZrO2 上沉积一定量的正硅酸四乙酯（TEOS）而制备的。与丙烯低聚催化剂性能较差的未改性氧化物相比，SiO2-MOx 材料表现出适度的活性，其中 Al2O3、TiO2 和 Nb2O5 核心材料的比表面积表现优于商用无定形二氧化硅氧化铝 (ASA)。根据 31P TMPO MAS NMR 测量，材料的活性似乎主要受其勃氏酸强度的影响，其速率依次为 SiO2/Al2O3 > SiO2/TiO2 ≈ SiO2/Nb2O5 > SiO2/ZrO2。这项研究表明，SiO2 涂层材料是一类可调的材料，对气相丙烯低聚具有活性。

{"title":"Propylene oligomerization over SiO2-overcoated oxides","authors":"Andrew T.Y. Wolek , Evan Sowinski , Rajamani Gounder , Justin M. Notestein","doi":"10.1016/j.jcat.2024.115820","DOIUrl":"10.1016/j.jcat.2024.115820","url":null,"abstract":"<div><div>Catalytic oligomerization of light olefins is an important C<img>C coupling strategy that can be used to produce high-value transportation fuels and chemicals from shale gas and biomass feedstocks. In this work, vapor-phase propylene oligomerization was studied over a series of overcoated SiO<sub>2</sub>-MOx materials, whose acid site densities and strengths are tunable by the amount of SiO<sub>2</sub> deposition and the nature of the core oxide. These materials contain acid sites only on particle external surfaces, limiting pore diffusion artifacts. SiO<sub>2</sub>-MOx materials were prepared by depositing stoichiometric amounts of tetraethyl orthosilicate (TEOS) onto Al<sub>2</sub>O<sub>3</sub>, anatase TiO<sub>2</sub>, Nb<sub>2</sub>O<sub>5</sub>, and ZrO<sub>2</sub>. Compared to the unmodified oxides, which are poor propylene oligomerization catalysts, the SiO<sub>2</sub>-MOx materials exhibit moderate activity with Al<sub>2</sub>O<sub>3</sub>, TiO<sub>2</sub>, and Nb<sub>2</sub>O<sub>5</sub> core materials performing better than commercial amorphous silica alumina (ASA) on a surface area basis. The activity of the materials appears to be primarily driven by their Brønsted acid strength as measured by <sup>31</sup>P TMPO MAS NMR with the rates ranked in order SiO<sub>2</sub>/Al<sub>2</sub>O<sub>3</sub> > SiO<sub>2</sub>/TiO<sub>2</sub> ≈ SiO<sub>2</sub>/Nb<sub>2</sub>O<sub>5</sub> > SiO<sub>2</sub>/ZrO<sub>2</sub>. This study shows that SiO<sub>2</sub>-overcoated materials are a tunable class of materials that are active for vapor-phase propylene oligomerization.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"440 ","pages":"Article 115820"},"PeriodicalIF":6.5,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142489084","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

Generation of alkene radical cation for thioxanthone-TfOH complex-catalyzed intramolecular cyclization using a photoredox catalysis strategy 利用光氧化催化策略生成硫黄酮-TfOH 复合物催化分子内环化的烯自由基阳离子

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2024-10-23 DOI: 10.1016/j.jcat.2024.115817

Jin Feng , Guanglong Huang , Haoliang Huang , Hanguang Tang , Wangsheng Liu , Aishun Ding , Xiao-Song Xue , Hao Guo

Photo catalysis has comprehensively become a powerful tool in organic synthesis, and organic molecules are thriving as catalyst. The thioxanthone-TfOH complex (9-HTXTF) as photoredox catalyst with high oxidative capacity can be applied in single electron reduction of alkene affording alkene radical anion as a key intermediate. To transform this intermediate from radical anion to radical cation, a well-designed strategy is proposed with N-arylacrylamides as substrate. Based on its single electron transfer (SET) with 9-HTXTF*, N-radical cation is generated and then transformed to alkene radical cation by intramolecular conjugated system. By using this photoredox catalysis strategy, we developed a 9-HTXTF-catalyzed photochemical cyclization of alkenes, which further expands the applications of this catalyst. The entire cyclization is metal-free and without sacrificing agents, which conforms to atom economy and environmental friendliness.

光催化已全面成为有机合成的有力工具，而有机分子作为催化剂的作用也在蓬勃发展。作为具有高氧化能力的光氧化催化剂，硫氧杂环酮-TfOH 复合物（9-HTXTF）可用于烯的单电子还原反应，生成烯自由基阴离子作为关键中间体。为了将该中间体从自由基阴离子转化为自由基阳离子，我们提出了一种以 N-芳基丙烯酰胺为底物的精心设计的策略。根据其与 9-HTXTF* 的单电子转移（SET），生成 N-自由基阳离子，然后通过分子内共轭体系转化为烯自由基阳离子。利用这种光氧化催化策略，我们开发出了 9-HTXTF 催化的烯烃光化学环化反应，进一步拓展了该催化剂的应用领域。整个环化过程不需要金属，也不需要牺牲药剂，符合原子经济性和环境友好性的要求。

{"title":"Generation of alkene radical cation for thioxanthone-TfOH complex-catalyzed intramolecular cyclization using a photoredox catalysis strategy","authors":"Jin Feng , Guanglong Huang , Haoliang Huang , Hanguang Tang , Wangsheng Liu , Aishun Ding , Xiao-Song Xue , Hao Guo","doi":"10.1016/j.jcat.2024.115817","DOIUrl":"10.1016/j.jcat.2024.115817","url":null,"abstract":"<div><div>Photo catalysis has comprehensively become a powerful tool in organic synthesis, and organic molecules are thriving as catalyst. The thioxanthone-TfOH complex (<strong>9-HTXTF</strong>) as photoredox catalyst with high oxidative capacity can be applied in single electron reduction of alkene affording alkene radical anion as a key intermediate. To transform this intermediate from radical anion to radical cation, a well-designed strategy is proposed with <em>N</em>-arylacrylamides as substrate. Based on its single electron transfer (SET) with <strong>9-HTXTF</strong>*, N-radical cation is generated and then transformed to alkene radical cation by intramolecular conjugated system. By using this photoredox catalysis strategy, we developed a <strong>9-HTXTF</strong>-catalyzed photochemical cyclization of alkenes, which further expands the applications of this catalyst. The entire cyclization is metal-free and without sacrificing agents, which conforms to atom economy and environmental friendliness.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"440 ","pages":"Article 115817"},"PeriodicalIF":6.5,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142488177","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

Electron-withdrawing effect of polyoxometalates in Cu(I)-based metal–organic frameworks for enhanced azide-alkyne “click” reaction Cu(I)-based metal-organic frameworks（铜铟金属有机框架）中多氧金属酸盐的电子吸附效应促进叠氮-炔烃 "点击 "反应

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2024-10-22 DOI: 10.1016/j.jcat.2024.115818

Bing-Bing Lu , Ji-Qiang Guan , Yu-Tong Wu , Si-Yi An , Ying Fu , Fei Ye

Boosting the nucleophilicity of Cu(I) sites is an essential strategy to enhance the efficiency of Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. In this work, a Lindquist-type polyoxometalate (POM)-based metal–organic framework, [Cu^I₄(W₆O₁₉)₂(L)]·2H₂O (NEAU-1), was synthesized via an in-situ solvothermal method. Single-crystal X-ray diffraction results reveal that NEAU-1 exhibits a sandwich structure, with POMs intercalated between the two-dimensional layers formed by resorcin[4]arene ligands and Cu(I) ions. NEAU-1 possesses abundant Cu(I) active sites and high chemical stability, making it an effective heterogeneous catalyst for the CuAAC reaction. More importantly, the presence of POMs effectively reduces the electron cloud density around Cu(I) sites, significantly lowering the energy barrier for the formation of copper-acetylide compounds and facilitating subsequent nucleophilic reactions. The synergistic catalytic effect of POMs and Cu(I) can achieve a conversion rate of over 99 % for benzyl azide and phenylacetylene within 40 min. This work presents a sustainable molecular-level strategy to enhance the activity of the CuAAC reaction.

提高 Cu（I）位点的亲核性是提高 Cu（I）催化的叠氮-炔环加成反应（CuAAC）效率的基本策略。本研究采用原位溶热法合成了一种基于林奎斯特型聚氧化金属（POM）的金属有机框架[CuI4(W6O19)2(L)]-2H2O（NEAU-1）。单晶 X 射线衍射结果表明，NEAU-1 呈夹层结构，在间苯二酚[4]炔配体和铜（I）离子形成的二维层之间夹有 POM。NEAU-1 具有丰富的 Cu(I) 活性位点和较高的化学稳定性，使其成为 CuAAC 反应的有效异相催化剂。更重要的是，POMs 的存在有效降低了 Cu（I）位点周围的电子云密度，显著降低了形成铜乙酰化合物的能障，促进了后续的亲核反应。在 POMs 和 Cu(I) 的协同催化作用下，苄基叠氮化物和苯乙炔在 40 分钟内的转化率可达 99% 以上。这项工作提出了一种可持续的分子级策略，以提高 CuAAC 反应的活性。

{"title":"Electron-withdrawing effect of polyoxometalates in Cu(I)-based metal–organic frameworks for enhanced azide-alkyne “click” reaction","authors":"Bing-Bing Lu , Ji-Qiang Guan , Yu-Tong Wu , Si-Yi An , Ying Fu , Fei Ye","doi":"10.1016/j.jcat.2024.115818","DOIUrl":"10.1016/j.jcat.2024.115818","url":null,"abstract":"<div><div>Boosting the nucleophilicity of Cu(I) sites is an essential strategy to enhance the efficiency of Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. In this work, a Lindquist-type polyoxometalate (POM)-based metal–organic framework, [Cu<sup>I</sup><sub>4</sub>(W<sub>6</sub>O<sub>19</sub>)<sub>2</sub>(L)]·2H<sub>2</sub>O (NEAU-1), was synthesized via an in-situ solvothermal method. Single-crystal X-ray diffraction results reveal that NEAU-1 exhibits a sandwich structure, with POMs intercalated between the two-dimensional layers formed by resorcin[4]arene ligands and Cu(I) ions. NEAU-1 possesses abundant Cu(I) active sites and high chemical stability, making it an effective heterogeneous catalyst for the CuAAC reaction. More importantly, the presence of POMs effectively reduces the electron cloud density around Cu(I) sites, significantly lowering the energy barrier for the formation of copper-acetylide compounds and facilitating subsequent nucleophilic reactions. The synergistic catalytic effect of POMs and Cu(I) can achieve a conversion rate of over 99 % for benzyl azide and phenylacetylene within 40 min. This work presents a sustainable molecular-level strategy to enhance the activity of the CuAAC reaction.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"440 ","pages":"Article 115818"},"PeriodicalIF":6.5,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486829","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

Highly stable and electron-rich Ni single atom catalyst for directed electroreduction of CO2 to CO 将二氧化碳定向电还原为二氧化碳的高稳定性富电子镍单原子催化剂

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2024-10-21 DOI: 10.1016/j.jcat.2024.115815

Fengwei Zhang , Jijie Li , Shuai Chen , Jingjing Li , Ruimin Zhang , Yangyang Zhao , Wen-Yan Zan , Yawei Li

Transition metal-nitrogen-carbon (M−N−C) are considered as promising candidates for the electrochemical conversion of inert CO₂ into high value-added CO products. However, previous reports have focused on Ni single-atom sites (Ni SAs) and the role of Ni nanoparticles (Ni NPs) in CO₂ electroreduction reaction (CO₂RR) has been overlooked. Herein, we prepared a series of Ni, N-codoped porous carbon (NiNC-T, T represents the temperature) catalysts by combining Ni phthalocyanine pyrolysis and acid etching strategy, which either contain only Ni SAs or both Ni SAs and Ni NPs. Notably, the NiNC-1100 catalyst with both Ni SAs and Ni NPs exhibited 99 % CO faradaic efficiency (FE_CO) at −0.66 V versus reversible hydrogen electrode (vs. RHE) and FE_CO above 98 % over a wide potential range (−0.66 V ∼ −1.06 V). Moreover, the FE_CO of NiNC-1100 remained above 95 % after 100 h of continuous electrocatalysis, which was significantly superior to that of the most advanced Ni single atom electrocatalysts. The systematic characterization results showed that the introduction of Ni NPs can promote the adsorption and activation of CO₂ by increasing the electron cloud density of Ni SAs, thus enhancing the CO₂RR catalytic performance.

过渡金属氮碳（M-N-C）被认为是将惰性二氧化碳电化学转化为高附加值一氧化碳产品的理想候选材料。然而，以往的报道主要集中于镍单原子位点（Ni SA），而镍纳米颗粒（Ni NPs）在 CO2 电还原反应（CO2RR）中的作用却被忽视了。在此，我们结合镍酞菁热解和酸蚀策略，制备了一系列镍、N-掺杂多孔碳（NiNC-T，T 代表温度）催化剂，这些催化剂或仅含有镍单原子位点，或同时含有镍单原子位点和镍纳米粒子。值得注意的是，同时含有 Ni SAs 和 Ni NPs 的 NiNC-1100 催化剂在 -0.66 V 相对于可逆氢电极（vs. RHE）时的 CO 法拉第效率（FECO）为 99%，在较宽的电位范围（-0.66 V ∼ -1.06 V）内的 FECO 均高于 98%。此外，在连续电催化 100 小时后，NiNC-1100 的 FECO 仍保持在 95% 以上，明显优于最先进的镍单原子电催化剂。系统表征结果表明，Ni NPs 的引入可以通过增加 Ni SAs 的电子云密度来促进 CO2 的吸附和活化，从而提高 CO2RR 催化性能。

{"title":"Highly stable and electron-rich Ni single atom catalyst for directed electroreduction of CO2 to CO","authors":"Fengwei Zhang , Jijie Li , Shuai Chen , Jingjing Li , Ruimin Zhang , Yangyang Zhao , Wen-Yan Zan , Yawei Li","doi":"10.1016/j.jcat.2024.115815","DOIUrl":"10.1016/j.jcat.2024.115815","url":null,"abstract":"<div><div>Transition metal-nitrogen-carbon (M−N−C) are considered as promising candidates for the electrochemical conversion of inert CO<sub>2</sub> into high value-added CO products. However, previous reports have focused on Ni single-atom sites (Ni SAs) and the role of Ni nanoparticles (Ni NPs) in CO<sub>2</sub> electroreduction reaction (CO<sub>2</sub>RR) has been overlooked. Herein, we prepared a series of Ni, N-codoped porous carbon (NiNC-T, T represents the temperature) catalysts by combining Ni phthalocyanine pyrolysis and acid etching strategy, which either contain only Ni SAs or both Ni SAs and Ni NPs. Notably, the NiNC-1100 catalyst with both Ni SAs and Ni NPs exhibited 99 % CO faradaic efficiency (FE<sub>CO</sub>) at −0.66 V versus reversible hydrogen electrode (<em>vs.</em> RHE) and FE<sub>CO</sub> above 98 % over a wide potential range (−0.66 V ∼ −1.06 V). Moreover, the FE<sub>CO</sub> of NiNC-1100 remained above 95 % after 100 h of continuous electrocatalysis, which was significantly superior to that of the most advanced Ni single atom electrocatalysts. The systematic characterization results showed that the introduction of Ni NPs can promote the adsorption and activation of CO<sub>2</sub> by increasing the electron cloud density of Ni SAs, thus enhancing the CO<sub>2</sub>RR catalytic performance.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"440 ","pages":"Article 115815"},"PeriodicalIF":6.5,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452585","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

Anion intercalation of NiMn-LDH accelerating urea electrooxidation on trivalent nickel NiMn-LDH 的阴离子插层加速三价镍上的尿素电氧化作用

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2024-10-21 DOI: 10.1016/j.jcat.2024.115814

Qian Zheng , Yuandong Yan , Shaonan Zhang , Shicheng Yan , Zhigang Zou

Reducing the urea oxidation reaction (UOR) barriers is a key knot for accelerating its practical applications. Here, we demonstrate that NiMn-LDH with sulfate anion interaction can enable urea electrooxidation with a low anodic potential of 1.36 V at 100 mA cm⁻². We find that the UOR on NiMn-LDH is driven by Ni³⁺ species and the Ni³⁺ generation is the rate-determining step of UOR. Both the Mn doping and sulfate anion interaction contribute to the low-barrier phase transformation from Ni(OH)₂ to NiOOH to produce the Ni³⁺ state with high activity in UOR, owing to that Mn doping optimizes the electronic states and intercalation of guest anions weakens the interlayer interactions, which ultimately tunes Ni³⁺ generation kinetics toward the superior UOR activity. Our findings provide new insights into the design of the highly active UOR catalysts.

降低尿素氧化反应（UOR）的障碍是加速其实际应用的关键。在此，我们证明了与硫酸根阴离子相互作用的 NiMn-LDH 可在 100 mA cm-2 条件下以 1.36 V 的低阳极电位实现尿素电氧化。我们发现，NiMn-LDH 上的尿素电氧化是由 Ni3+ 物种驱动的，Ni3+ 的生成是尿素电氧化的决定性步骤。掺杂锰和硫酸根阴离子的相互作用都有助于从 Ni(OH)2 到 NiOOH 的低势垒相变，从而在 UOR 中产生具有高活性的 Ni3+ 态，这是因为掺杂锰优化了电子态，而客体阴离子的插层削弱了层间相互作用，最终调整了 Ni3+ 生成动力学，使其具有更高的 UOR 活性。我们的发现为高活性 UOR 催化剂的设计提供了新的思路。

引用次数: 0

首页上一页

下一页尾页

类型

全部化学•材料生命科学医学物理工程技术环境•农林材料科学地球科学法学管理学化学环境科学与生态学计算机科学教育学经济学农林科学人文科学生物学数学物理与天体物理心理学综合性期刊其他工业工程理学历史学农学文学信息工程

数据库

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

期刊

Journal of Catalysis

全部 Acc. Chem. Res. ACS Applied Bio Materials ACS Appl. Electron. Mater. ACS Appl. Energy Mater. ACS Appl. Mater. Interfaces ACS Appl. Nano Mater. ACS Appl. Polym. Mater. ACS BIOMATER-SCI ENG ACS Catal. ACS Cent. Sci. ACS Chem. Biol. ACS Chemical Health & Safety ACS Chem. Neurosci. ACS Comb. Sci. ACS Earth Space Chem. ACS Energy Lett. ACS Infect. Dis. ACS Macro Lett. ACS Mater. Lett. ACS Med. Chem. Lett. ACS Nano ACS Omega ACS Photonics ACS Sens. ACS Sustainable Chem. Eng. ACS Synth. Biol. Anal. Chem. BIOCHEMISTRY-US Bioconjugate Chem. BIOMACROMOLECULES Chem. Res. Toxicol. Chem. Rev. Chem. Mater. CRYST GROWTH DES ENERG FUEL Environ. Sci. Technol. Environ. Sci. Technol. Lett. Eur. J. Inorg. Chem. IND ENG CHEM RES Inorg. Chem. J. Agric. Food. Chem. J. Chem. Eng. Data J. Chem. Educ. J. Chem. Inf. Model. J. Chem. Theory Comput. J. Med. Chem. J. Nat. Prod. J PROTEOME RES J. Am. Chem. Soc. LANGMUIR MACROMOLECULES Mol. Pharmaceutics Nano Lett. Org. Lett. ORG PROCESS RES DEV ORGANOMETALLICS J. Org. Chem. J. Phys. Chem. J. Phys. Chem. A J. Phys. Chem. B J. Phys. Chem. C J. Phys. Chem. Lett. Analyst Anal. Methods Biomater. Sci. Catal. Sci. Technol. Chem. Commun. Chem. Soc. Rev. CHEM EDUC RES PRACT CRYSTENGCOMM Dalton Trans. Energy Environ. Sci. ENVIRON SCI-NANO ENVIRON SCI-PROC IMP ENVIRON SCI-WAT RES Faraday Discuss. Food Funct. Green Chem. Inorg. Chem. Front. Integr. Biol. J. Anal. At. Spectrom. J. Mater. Chem. A J. Mater. Chem. B J. Mater. Chem. C Lab Chip Mater. Chem. Front. Mater. Horiz. MEDCHEMCOMM Metallomics Mol. Biosyst. Mol. Syst. Des. Eng. Nanoscale Nanoscale Horiz. Nat. Prod. Rep. New J. Chem. Org. Biomol. Chem. Org. Chem. Front. PHOTOCH PHOTOBIO SCI PCCP Polym. Chem.

﹀