Kinetics and Catalysis最新文献_第8页

Ammonia Synthesis and Decomposition in the Presence of Supported Ruthenium Catalysts 有载体钌催化剂存在时的氨合成和分解

IF 1.3 4区化学

Kinetics and Catalysis Pub Date : 2023-12-12 DOI: 10.1134/S0023158423060137

D. A. Shlyapin, V. A. Borisov, V. L. Temerev, K. N. Iost, Z. A. Fedorova, P. V. Snytnikov

{"title":"Ammonia Synthesis and Decomposition in the Presence of Supported Ruthenium Catalysts","authors":"D. A. Shlyapin, V. A. Borisov, V. L. Temerev, K. N. Iost, Z. A. Fedorova, P. V. Snytnikov","doi":"10.1134/S0023158423060137","DOIUrl":"10.1134/S0023158423060137","url":null,"abstract":"Based on analysis of the catalytic properties of 4%Ru–13.6%Cs/Sibunit and 4%Ru–5.4%Ba–7.9%Cs/Sibunit in the ammonia decomposition (105 Pa, 350–470°C) and ammonia synthesis processes (6 × 105–5 × 106 Pa, 400–430°C), an analytical expression for nitrogen formation/consumption rate in the reversible reaction N2 + 3H2 ( rightleftharpoons ) 2NH3 has been derived to correctly describe the dependence of the chemical reaction rate on the partial pressures of the reaction mixture components for both the forward and reverse reactions. The approach used to derive the kinetic equation is based on the assumption that the adsorption sites of the ruthenium surface are filled with hydrogen, which is subsequently displaced by nitrogen during competitive interaction. Using the proposed kinetic equation, the equilibrium constants and apparent activation energies for ammonia synthesis and decomposition in the presence of 4%Ru–13.6%Cs/Sibunit and 4%Ru–5.4%Ba–7.9%Cs/Sibunit catalysts have been determined; the values are in good agreement with the published data.","PeriodicalId":682,"journal":{"name":"Kinetics and Catalysis","volume":"64 6","pages":"815 - 825"},"PeriodicalIF":1.3,"publicationDate":"2023-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138575238","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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

Cu–Ni/SiO2 Catalysts for Dehydrogenation Reaction of Secondary Butyl Alcohol 用于仲丁醇脱氢反应的铜镍/二氧化硅催化剂

IF 1.3 4区化学

Kinetics and Catalysis Pub Date : 2023-12-12 DOI: 10.1134/S0023158423930031

Li Zhang, Yujing Xue, Ying Zhang

{"title":"Cu–Ni/SiO2 Catalysts for Dehydrogenation Reaction of Secondary Butyl Alcohol","authors":"Li Zhang, Yujing Xue, Ying Zhang","doi":"10.1134/S0023158423930031","DOIUrl":"10.1134/S0023158423930031","url":null,"abstract":"Cu–Ni/SiO2 catalysts were prepared by coprecipitation method and used in the dehydrogenation reaction of secondary butyl alcohol to methyl ethyl ketone (MEK). The crystal structure, reduction characteristics, element valence state and dispersibility of the catalysts were investigated using X-ray diffraction (XRD), hydrogen temperature-programmed reduction (H2-TPR), inductively coupled plasma optical emission spectrometry (ICP-OES), X-ray photoelectron spectroscopy (XPS), X-ray Auger electron spectroscopy (XAES) and high resolution transmission electron microscopy (HRTEM). The role of Ni component in the dehydrogenation reaction of secondary butyl alcohol was analyzed. The results showed that the conversion of secondary butyl alcohol increased to over 99% when using the Cu–Ni/SiO2 catalyst. The addition of nickel component to Cu/SiO2 inhibited the agglomeration of copper nanoparticles. The interaction between copper and nickel was strengthened due to the formation of the Cu–Ni compound. This resulted in change to the valence state and improved the dispersion of copper species on the catalyst surface. The Cu+/(Cu+ + Cu0) ratio increased with the addition of nickel component to Cu/SiO2, which may be responsible for the enhancement of the secondary butyl alcohol conversion. However, the addition of the nickel component increased the reduction temperature of the catalysts and deteriorated their reduction characteristics, which leads to insufficient reduction, resulting in a high content of Cu+ species remaining in the catalyst. Therefore, side reactions can occur, which are detrimental to the selectivity and yield of MEK. The selectivity to MEK can reach 98% with the Cu/SiO2 catalyst, whereas that for the Cu–Ni/SiO2 catalyst was 97%.","PeriodicalId":682,"journal":{"name":"Kinetics and Catalysis","volume":"64 6","pages":"872 - 881"},"PeriodicalIF":1.3,"publicationDate":"2023-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138575876","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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

The First Application of Palladium–Phosphorus Catalysts in the Direct Synthesis of Hydrogen Peroxide: Reasons for the Promoting Action of Phosphorus 钯磷催化剂在直接合成过氧化氢中的首次应用：磷的促进作用的原因

IF 1.3 4区化学

Kinetics and Catalysis Pub Date : 2023-12-12 DOI: 10.1134/S0023158423060022

L. B. Belykh, N. I. Skripov, T. P. Sterenchuk, V. V. Akimov, V. L. Tauson, M. N. Likhatski, E. A. Milenkaya, T. A. Kornaukhova, F. K. Schmidt

{"title":"The First Application of Palladium–Phosphorus Catalysts in the Direct Synthesis of Hydrogen Peroxide: Reasons for the Promoting Action of Phosphorus","authors":"L. B. Belykh, N. I. Skripov, T. P. Sterenchuk, V. V. Akimov, V. L. Tauson, M. N. Likhatski, E. A. Milenkaya, T. A. Kornaukhova, F. K. Schmidt","doi":"10.1134/S0023158423060022","DOIUrl":"10.1134/S0023158423060022","url":null,"abstract":"The main reasons for the promoting effect of phosphorus on the properties of Pd–P/ZSM-5 catalysts during direct synthesis of H2O2 from H2 and O2 under mild conditions are considered based on the data obtained by X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), and inductively coupled plasma mass spectrometry (ICP MS). The introduction of phosphorus in the catalyst affects the particle size and the electronic state of palladium in the surface layer, as well as the surface concentration of the phosphate and phosphite ions. The yield of H2O2 increases when the particle size of the Pd–P catalysts decreases, when the side process of H2O2 decomposition is inhibited by the phosphate and phosphite surface ions, and when the hydrogen solubility in the solid solutions of phosphorus in palladium decreases.","PeriodicalId":682,"journal":{"name":"Kinetics and Catalysis","volume":"64 6","pages":"804 - 814"},"PeriodicalIF":1.3,"publicationDate":"2023-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138575320","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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

Variation of the Catalytic Activity and Selectivity of Cobalt in Ethylene Oxidation during Stepwise Oxidation of the Cobalt Surface 钴表面逐步氧化过程中钴在乙烯氧化过程中的催化活性和选择性变化

IF 1.3 4区化学

Kinetics and Catalysis Pub Date : 2023-12-12 DOI: 10.1134/S0023158423060046

V. Yu. Bychkov, Yu. P. Tulenin, A. A. Gulin, V. N. Korchak

{"title":"Variation of the Catalytic Activity and Selectivity of Cobalt in Ethylene Oxidation during Stepwise Oxidation of the Cobalt Surface","authors":"V. Yu. Bychkov, Yu. P. Tulenin, A. A. Gulin, V. N. Korchak","doi":"10.1134/S0023158423060046","DOIUrl":"10.1134/S0023158423060046","url":null,"abstract":"The dependence of the catalytic activity of Co foil in ethylene oxidation on the degree of oxidation of the Co surface during stepwise oxidation of foil has been studied. The experiments were performed at 500–800°C by the pulse method using alternating pulses of a 0.2%C2H4–0.25%O2–1%Ar–He test mixture and a 1%O2–1%Ar–He oxidative mixture. The degree of oxidation of the Co foil surface varied from total reduction to oxidation of ~100 cobalt oxide “monolayers.” The XRD, SEM, and EDS studies showed that CoO formed at the first stage of stepwise oxidation (from 0 to ~60 oxide “monolayers”) at all temperatures under study, and changes in the surface morphology could be observed. In this state the samples had a relatively high activity in both partial and total oxidation of ethylene at 500–600°C. At 700–800°C, however, there was no total oxidation, and the rate of partial oxidation was much lower than at 500–600°C. At the second stage of Co surface oxidation (from ~60 to ~120 oxide “monolayers”) at 500–600°C, Co3O4 formed, and gradual ordering of oxide crystals was observed. In this state, the samples exhibited constant (at 500°C) or extreme (at 600°C) activity in the total oxidation of ethylene. In contrast, an increase in the temperature to 800°C led to a drastic decrease in the catalytic activity of Co foil in the given range of the degrees of oxidation.","PeriodicalId":682,"journal":{"name":"Kinetics and Catalysis","volume":"64 6","pages":"837 - 848"},"PeriodicalIF":1.3,"publicationDate":"2023-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138614646","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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

Homogeneous Redox Catalysts Based on Heteropoly Acid Solutions: 5. Developing a Two-Stage Process for Propylene Oxidation to Acetone: A Review 基于杂多酸溶液的均相氧化还原催化剂：5.开发丙烯氧化制丙酮的两阶段工艺：综述

IF 1.3 4区化学

Kinetics and Catalysis Pub Date : 2023-12-12 DOI: 10.1134/S0023158423060125

Yu. A. Rodikova, E. G. Zhizhina

{"title":"Homogeneous Redox Catalysts Based on Heteropoly Acid Solutions: 5. Developing a Two-Stage Process for Propylene Oxidation to Acetone: A Review","authors":"Yu. A. Rodikova, E. G. Zhizhina","doi":"10.1134/S0023158423060125","DOIUrl":"10.1134/S0023158423060125","url":null,"abstract":"Studies on the development of a homogeneous chloride-free two-stage process (target reaction (first stage) and catalyst regeneration (second stage)) for propylene oxidation to acetone with oxygen in the presence of a ({text{Pd}}_{{{text{aq}}}}^{{{text{2 + }}}}) + Mo–V–P heteropoly acid (HPA-x, where x is the number of V atoms) catalyst have been described. A kinetic equation of the target reaction has been derived; a mechanism of the reaction has been proposed. It has been shown that the most efficient catalysts are those based on high-vanadium modified (non-Keggin) HPA-xM compositions. It has been found that the kinetics of C3H6 oxidation in the presence of Keggin HPA-x and HPA-xM solutions is identical; however, only ({text{Pd}}_{{{text{aq}}}}^{{{text{2 + }}}}) + HPA-xM catalysts are technologically feasible. They exhibit high thermal stability (up to 180°C) and, therefore, can be rapidly regenerated with oxygen. Owing to this feature, catalysts based on HPA-xM compare favorably with those based on Keggin HPAs-x, the thermal stability of which is limited to 140°C. The possibility of rapidly regenerating the catalyst has made it possible to close the two-stage catalytic cycle of C3H6 oxidation to acetone with oxygen and opened up prospects for the practical implementation of the process in the presence of ({text{Pd}}_{{{text{aq}}}}^{{{text{2 + }}}}) + HPA-xM. The catalyst has effectively passed stability tests.","PeriodicalId":682,"journal":{"name":"Kinetics and Catalysis","volume":"64 6","pages":"687 - 699"},"PeriodicalIF":1.3,"publicationDate":"2023-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138616372","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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

Using SAXS for Determining the Sizes of Gold Nanoparticles in Au/C Catalysts: Advantages over Other Methods 使用 SAXS 测定 Au/C 催化剂中金纳米粒子的尺寸：与其他方法相比的优势

IF 1.3 4区化学

Kinetics and Catalysis Pub Date : 2023-12-12 DOI: 10.1134/S0023158423060083

Yu. V. Larichev, B. L. Moroz, P. A. Pyrjaev, V. I. Bukhtiyarov

引用次数: 0

Evaluation of the Catalytic Activities of Supported Copper Catalysts Surrounded with Different Functional Groups by o-Ps Annihilation 通过 o-Ps 湮灭评估不同官能团包围的支撑铜催化剂的催化活性

IF 1.3 4区化学

Kinetics and Catalysis Pub Date : 2023-12-12 DOI: 10.1134/S002315842393002X

Linbo Li, Yijun Du, Yao Li, Linjun Shao, Chenze Qi, Shujing Zhou, Jinjing Li

{"title":"Evaluation of the Catalytic Activities of Supported Copper Catalysts Surrounded with Different Functional Groups by o-Ps Annihilation","authors":"Linbo Li, Yijun Du, Yao Li, Linjun Shao, Chenze Qi, Shujing Zhou, Jinjing Li","doi":"10.1134/S002315842393002X","DOIUrl":"10.1134/S002315842393002X","url":null,"abstract":"Developing a facile and accurate method for assessing catalytic activities of supported metals can significantly promote the preparation and application of supported metal catalysts. Herein, we synthesized five MCM-41 materials functionalized with Schiff-base groups, which were employed as the supports for copper cations. The chemical structures and coordination of copper cations on the supports were characterized by Fourier-transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The grafting densities were calculated by analyzing the results of thermal gravimetric analysis (TGA) and elemental analysis (EA). The microstructures of these supported copper catalysts were analyzed by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The oxidation of thioanisole to methylphenyl sulfoxide was employed to determine the catalytic activities of these supported copper catalysts while their o-Ps annihilation properties were evaluated by the positron annihilation lifetime spectroscopy. It is found that the o-Ps annihilation properties were linearly correlated with their catalytic activities. Therefore, the catalytic activities of supported copper species surrounded by different functional groups can be easily determined through o-Ps annihilation.","PeriodicalId":682,"journal":{"name":"Kinetics and Catalysis","volume":"64 6","pages":"909 - 921"},"PeriodicalIF":1.3,"publicationDate":"2023-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138575316","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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, Mechanism, and Reactivity of Intermediates of the Cerium(IV)–Oxalate Reaction in a Sulfate Medium 硫酸盐介质中铈(IV)-草酸反应中间产物的动力学、机理和反应活性

IF 1.3 4区化学

Kinetics and Catalysis Pub Date : 2023-12-12 DOI: 10.1134/S0023158423060186

O. O. Voskresenskaya, N. A. Skorik

{"title":"Kinetics, Mechanism, and Reactivity of Intermediates of the Cerium(IV)–Oxalate Reaction in a Sulfate Medium","authors":"O. O. Voskresenskaya, N. A. Skorik","doi":"10.1134/S0023158423060186","DOIUrl":"10.1134/S0023158423060186","url":null,"abstract":"The work presents an approach for studying the kinetics, mechanism, and reactivity of intermediates of a wide class of redox reactions for which the rate-limiting step is the redox decomposition of the intermediate complex. The approach was applied to the investigation of the oxidation of oxalic acid (H2Ox) by cerium(IV) in a sulfuric acid medium as part of the Belousov–Zhabotinsky oscillating reaction (BZ reaction) catalyzed by cerium ions. Experimental, mathematical, and computational methods that are typically used to study metal complexes in a stable oxidation state were kinetically generalized to variable-valence metal complexes and were used to determine the characteristics of intermediate complexes of the cerium(IV)–oxalate reaction and derive a general equation for its rate based on a set of equations describing the rapid achievement of pre-equilibrium in the system and the subsequent nonequilibrium process. A quantitative model of the process was proposed; it included two parallel reaction pathways, for which two different cerium(IV)–oxalate intermediate complexes were identified and characterized. The complexes have similar reactivity, which may be due to the similarity of the structure of their inner coordination spheres and the inner-sphere mechanism of electron transfer in the complexes. Using the developed model, a diagram of the yields of all main species of cerium(IV) under the conditions of the BZ reaction was constructed, which indicates the need to take into account the formation of intermediate complexes of the composition CeOHOx(_{n}^{{3 - 2n}}) (n = 1, 2) in the oxidation of oxalic acid under these conditions. The main difference between the presented model of the cerium(IV)–oxalate reaction as part of the BZ reaction and the previous models is the explicit consideration of the participation of intermediate complexes of cerium(IV) with oxalic acid anions and sulfate background anions in the reaction.","PeriodicalId":682,"journal":{"name":"Kinetics and Catalysis","volume":"64 6","pages":"729 - 740"},"PeriodicalIF":1.3,"publicationDate":"2023-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138575309","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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

Distinguishing Between Linear and Nonlinear (Cooperative) Mechanisms of Substrate Activation Under “Ligand- and Copper-Free” Conditions of the Sonogashira Reaction 区分在 "配体和无铜 "条件下子桥反应底物活化的线性和非线性（合作）机制

IF 1.3 4区化学

Kinetics and Catalysis Pub Date : 2023-12-12 DOI: 10.1134/S0023158423060095

E. V. Larina, A. A. Kurokhtina, N. A. Lagoda, A. F. Schmidt

引用次数: 0

Impact of Ethanol Blending Ratios on the Unregulated Emissions Issued from the Combustion of Diesel–Biodiesel–Ethanol Mixtures 乙醇混合比对柴油-生物柴油-乙醇混合物燃烧产生的非规范排放物的影响

IF 1.3 4区化学

Kinetics and Catalysis Pub Date : 2023-12-12 DOI: 10.1134/S0023158423060113

Y. Rezgui, M. Guemini, A. Tighezza

引用次数: 0