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Synthesis and Characterization of Faujasite/ZIF-8 Composite by One-Pot Method, Used as a Catalyst for Esterification and Aldol Condensation Reaction 单锅法合成并表征用作酯化和醛缩合反应催化剂的褐铁矿/ZIF-8 复合材料
IF 2.1 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2023-12-08 DOI: 10.1007/s10563-023-09417-8
Hadis Ghaedrahmat, Mohammad Yaser Masoomi, Mojgan Zendehdel

In this research work, we were able to composite Faujasite type zeolite and ZIF-8 metal–organic framework using two different ways to improve the chemical stability of ZIF-8. In these methods, the arrangement of introducing Zn and 2-Methylimidazole as parent material to synthesis of ZIF-8 to zeolite were changed. In addition, the composites were prepared at room temperature under green chemistry conditions. The structure of Fauj/ZIF-8 nanocomposites were confirmed by FT-IR, XRD, SEM, BET, MAP, TGA, NH3-TPD and ICP analysis after synthesis. The Fauj/ZIF-8 nanocomposites with high acidity and micro-meso structure showed good stability. Two prepared composites were used as catalysts in organic reactions including esterification of acetic acid by four different alcohols and aldol condensation of benzaldehyde derivatives 2-X and 4-X. The results of these catalytic applications show that the use of nanocomposites yields is above 90% with good reusability under solvent free condition for esterification and aldol condensation reactions.

在这项研究工作中,我们采用两种不同的方法将 Faujasite 型沸石和 ZIF-8 金属有机框架复合在一起,以提高 ZIF-8 的化学稳定性。在这两种方法中,我们改变了将 Zn 和 2-甲基咪唑作为母体材料引入 ZIF-8 与沸石合成的排列方式。此外,复合材料是在室温绿色化学条件下制备的。合成后,通过傅立叶变换红外光谱、X射线衍射、扫描电镜、BET、MAP、TGA、NH3-TPD和ICP分析确认了Fauj/ZIF-8纳米复合材料的结构。具有高酸度和微介质结构的 Fauj/ZIF-8 纳米复合材料显示出良好的稳定性。制备的两种复合材料被用作有机反应的催化剂,包括四种不同醇对乙酸的酯化反应以及苯甲醛衍生物 2-X 和 4-X 的醛缩合反应。这些催化应用的结果表明,在无溶剂条件下,使用纳米复合材料进行酯化和醛缩合反应的产率在 90% 以上,并具有良好的重复使用性。
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引用次数: 0
Effect of Promoters (Co, Cr, Fe, Zr) on the Performance of MnO2/CeO2 Catalysts for NO Reduction at Low Temperatures Using NH3-SCR 促进剂(Co、Cr、Fe、Zr)对 MnO2/CeO2 催化剂在低温下利用 NH3-SCR 还原 NO 性能的影响
IF 2.1 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2023-12-07 DOI: 10.1007/s10563-023-09416-9
Shyam Sunder Rao, Sweta Sharma

This study examined the effect of various promoters (Co, Cr, Fe, Zr) in reducing NO using the NH3-SCR reaction on the MnO2/CeO2-Nanorod catalysts. The physicochemical properties of these catalysts were characterized using Brunauer–Emmett–Teller, X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscope, scanning electron microscope-energy dispersive X-ray spectroscopy, and Raman spectroscopy. Characterization analysis revealed uniform dispersion of active metals on CeO2-Nanorod supports, desired active metal-support synergism, small crystallite sizes, high specific surface areas, and an appreciable amount of surface lattice oxygen in Co–MnO2/CeO2-Nanorod catalysts. Co–MnO2/CeO2-Nanorod catalyst showed the best NH3-SCR activity at low temperatures. The NO conversion and N2 selectivity are 87 and 85%, respectively, at 300 °C with excellent stability. The Co–MnO2/CeO2-Nanorod catalyst also showed excellent tolerance against the H2O and the SO2. The catalyst’s performance can be attributed to its high surface area, oxygen storage capacity, high Ce3+ content, and evenly distributed promoters.

本研究考察了各种促进剂(Co、Cr、Fe、Zr)在 MnO2/CeO2-Nanorod 催化剂上利用 NH3-SCR 反应还原 NO 的效果。使用布鲁瑙尔-艾美特-泰勒、X 射线衍射、X 射线光电子能谱、透射电子显微镜、扫描电子显微镜-能量色散 X 射线光谱和拉曼光谱对这些催化剂的理化性质进行了表征。表征分析表明,Co-MnO2/CeO2-Nanorod 催化剂中的活性金属在 CeO2-Nanorod 载体上均匀分散,活性金属与载体之间具有理想的协同作用,结晶尺寸小,比表面积高,表面晶格氧含量可观。Co-MnO2/CeO2-Nanorod 催化剂在低温下表现出最佳的 NH3-SCR 活性。在 300 °C 下,NO 转化率和 N2 选择性分别为 87% 和 85%,且稳定性极佳。Co-MnO2/CeO2-Nanorod 催化剂对 H2O 和 SO2 的耐受性也很好。催化剂的性能得益于其高表面积、储氧能力、高 Ce3+ 含量和均匀分布的促进剂。
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引用次数: 0
Highly Active Mesoporous Zirconium Nitride Immobilized on SiO2 Synthesized by Complex-Assisted Method with EDTA and KHP for Catalytic Hydroconversion of Crude Palm Oil EDTA和KHP络合辅助法合成SiO2上高活性氮化锆催化棕榈油加氢转化
IF 2.1 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2023-11-25 DOI: 10.1007/s10563-023-09413-y
Wan Ryan Asri, Hasanudin Hasanudin, Karna Wijaya

This research aims to transform crude palm oil (CPO) into biofuels through a catalytic hydrocracking method using a SiO2–ZrN catalyst prepared by the chelate-assisted EDTA (ethylenediaminetetraacetic acid), denoted as SiO2–ZrN2 and KHP (potassium hydrogen phthalate), denoted as SiO2–ZrN3 catalysts, respectively. The as-prepared catalysts were characterized using XRD, FTIR, SEM-EDX mapping, PSA, gravimetric acidity analysis, and N2 adsorption–desorption. The transformation of SiO2–Zr to SiO2–ZrN through the nitriding treatment was able to change the particle size distribution of the catalyst from heterogeneous to homogeneous, as well as enhance the acidity the acidity and textural features with a highly dispersed ZrN on the silica. CPO hydrocracking test revealed that SiO2–ZrN prepared by chelate-assisted EDTA and KHP achieved high catalytic activity towards CPO hydroconversion followed by high liquid and low coke formation with an adequate stability performance. SiO2–ZrN successfully suppressed the formation of long-chain into short-chain hydrocarbon. Both SiO2–ZrN2 and SiO2–ZrN3 each exhibited a high fraction towards aviation fuel compared to parent SiO2 and SiO2–Zr.

本研究旨在通过催化加氢裂化方法将粗棕榈油(CPO)转化为生物燃料,使用螯合辅助EDTA(乙二胺四乙酸)制备的SiO2-ZrN催化剂,分别表示为SiO2-ZrN2和KHP(邻苯二甲酸氢钾),表示为SiO2-ZrN3催化剂。采用XRD、FTIR、SEM-EDX作图、PSA、重量酸度分析、N2吸附-脱附等方法对催化剂进行了表征。通过氮化处理将SiO2-Zr转变为SiO2-ZrN,使催化剂的粒径分布由多相转变为均相,并提高了催化剂的酸度和结构特征,使ZrN在二氧化硅上高度分散。实验结果表明,螯合EDTA和KHP制备的SiO2-ZrN对CPO加氢转化、高液低焦具有较高的催化活性,且具有良好的稳定性。SiO2-ZrN成功抑制了长链烃向短链烃的生成。相对于母体SiO2和SiO2 - zr, SiO2 - zrn2和SiO2 - zrn3均表现出较高的航空燃料分数。
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引用次数: 0
Enhanced Catalysis of Mechano-Chemically Synthesized KMgF3 Catalysts for the Knoevenagel Condensation 机械化学合成 KMgF3 催化剂在克诺文纳格尔缩合中的强化催化作用
IF 2.1 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2023-11-14 DOI: 10.1007/s10563-023-09412-z
Hajime Iida, Shouya Sugiyama, Tatsuya Horie

The catalytic activity of KMgF3 catalysts for a Knoevenagel condensation reaction was enhanced by synthesizing the catalysts mechano-chemically. The Brunauer–Emmett–Teller specific surface area and number of strongly basic site on KMgF3 were increased by applying greater mechanical energy (i.e. a higher rotation rate) during the mechano-chemical process. These increases were caused by stronger mechano-chemical effects such as micronization of the particles and the introduction of lattice defects onto the surface, which resulted in an enhancement of the catalytic activity of KMgF3 toward a Knoevenagel condensation reaction. X-ray photoelectron spectroscopic analysis revealed that the elemental composition of the KMgF3 surface was similar to that for K2MgF4, indicating the possibility that the true active component for this reaction was K2MgF4 rather than KMgF3. Kinetic measurements revealed that Knoevenagel condensation catalyzed by KMgF3 was a first-order reaction with an estimated apparent activation energy of 55.8 kJmol−1. A soluble component capable of acting as a catalyst was not present in the solution; the KMgF3 acted as a true solid catalyst.

通过机械化学合成 KMgF3 催化剂,提高了 KMgF3 在克诺文纳格尔缩合反应中的催化活性。在机械化学过程中,通过施加更大的机械能(即更高的旋转速率),KMgF3 上的布鲁瑙尔-艾美特-泰勒比表面积和强碱性位点数量都有所增加。这些增加是由更强的机械化学效应引起的,如颗粒的微粉化和表面晶格缺陷的引入,从而提高了 KMgF3 对克诺文纳格尔缩合反应的催化活性。X 射线光电子能谱分析表明,KMgF3 表面的元素组成与 K2MgF4 相似,这表明该反应的真正活性成分可能是 K2MgF4 而不是 KMgF3。动力学测量显示,KMgF3 催化的克诺文纳格尔缩合是一个一阶反应,表观活化能估计为 55.8 kJmol-1。溶液中不存在可作为催化剂的可溶性成分;KMgF3 是真正的固体催化剂。
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引用次数: 0
Synthesis of n-Butyl Levulinate Over Caesium Containing Heteropoly Acid Supported Zeolite β Catalysts 在含铯杂多酸支撑沸石 β 催化剂上合成乙酰丙酸正丁酯
IF 2.1 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2023-11-06 DOI: 10.1007/s10563-023-09410-1
Kalpana Maheria, Ramesh Kumar Chowdari, Janusz Kozinski, Ajay Kumar Dalai

The aim of the present work is to investigate an environmentally benign method for the catalytic conversion of biomass derived compounds into fine chemicals. Levulinic acid (LA) is one of the key biomass-derived chemicals that can be converted into biofuels and various other value-added chemicals. -Butyl levulinate ester is an important chemical used in the production of fuel additives, solvents, plasticizing agents, and odorous substances. The work presented here focused on the esterification of n-butyl levulinate by reaction of LA and n-butanol in the presence of synthesized 20% tungstophosphoric acid (TPA) supported zeolite β (TPA-Zβ), CsTPA-Zβ and Cs-Zβ catalysts. Various catalyst characterization techniques have been used, specifically, XRD, SEM–EDS, FT-IR, nitrogen physisorption and NH-TPD. The highest % yield of -butyl levulinate is obtained with shorter reaction time in the case of a 20% TPA supported zeolite β catalyst, calcined at 300 °C. The addition of Cs ions to TPA appears to improve catalytic performance.

Graphical Abstract

本研究的目的是探讨一种将生物质衍生化合物催化转化为精细化学品的无害环境方法。乙酰丙酸(LA)是一种重要的生物质衍生化学品,可转化为生物燃料和其他各种增值化学品。乙酰丙酸正丁酯是一种重要的化学品,可用于生产燃料添加剂、溶剂、增塑剂和异味物质。本文的研究重点是在合成的 20% 钨基磷酸(TPA)支撑沸石 β(TPA-Zβ)、CsTPA-Zβ 和 Cs-Zβ 催化剂存在下,通过 LA 和正丁醇的反应对左旋丙酸正丁酯进行酯化。使用了多种催化剂表征技术,特别是 XRD、SEM-EDS、FT-IR、氮物理吸附和 NH3 -TPD。在 300 °C 煅烧 20% 三羟甲基丙烷(TPA)支撑的沸石 β 催化剂时,反应时间较短,左旋丁酸正丁酯的产率最高。在 TPA 中添加铯离子似乎可以提高催化性能。
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引用次数: 0
Integrating Ni, Pt, and Pd on Biphasic Cu-Doped Bi2O3 for Physicochemical Characteristics and Superior Light Driven Elimination of Pollutants 在双相铜掺杂的 Bi2O3 上整合镍、铂和钯,以获得物理化学特性和卓越的光驱动污染物消除能力
IF 2.1 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2023-11-01 DOI: 10.1007/s10563-023-09411-0
Anuradha Sharma, Anuj Mittal, Shankar Sharma, Muhammad Tahir, Deepak Parmar, Pardeep Singh, Naveen Kumar

Fabrication of composite photocatalysts that provide an easy charge transfer mechanism to enhance the photocatalytic activity is a promising approach for the removal of organic contaminants from the water bodies. In this series, for the first time, we have decorated Ni, Pt, and Pd on the surface of hydrothermally synthesized Cu-doped biphasic Bi2O3. The synthesized composites were analyzed using advanced characterization techniques to uncover the physicochemical properties of the materials. The XRD results revealed well crystalline nature of the materials with enhanced particle size as compared to binary composite. The optical analysis showed the improved optical characteristics of ternary composites. The photocatalytic activity was tested against the RhB and observed the ternary materials with enhanced activity when compared with the binary composite and 5 wt% was the optimum loading of the metal on the surface of Cu- doped Bi2O3. Pd decorated samples showed the highest photo removal of RhB where complete mineralization of dye is achieved only in 50 min which is ascribed to the increased absorption and reduced reunion of charge carriers. The effect of pH of the reaction medium and the role of reactive oxygen species were also examined. In the acidic medium, complete degradation of dye is achieved in 10 min only and holes are found prominent active species for the degradation of RhB. The synthesized materials were stable and could be used many times without significant loss in the photocatalytic activity.

制作复合光催化剂,提供一种易于提高光催化活性的电荷转移机制,是去除水体中有机污染物的一种很有前景的方法。在这一系列研究中,我们首次在水热合成的掺铜双相 Bi2O3 表面装饰了镍、铂和钯。我们采用先进的表征技术对合成的复合材料进行了分析,以揭示材料的物理化学性质。XRD 结果表明,与二元复合材料相比,材料具有良好的结晶性和更大的粒度。光学分析表明,三元复合材料的光学特性得到改善。对 RhB 的光催化活性进行了测试,结果表明,与二元复合材料相比,三元材料的光催化活性更强。钯装饰的样品对 RhB 的光去除率最高,仅在 50 分钟内就实现了染料的完全矿化,这归因于电荷载体的吸收增加和重聚减少。还研究了反应介质 pH 值的影响和活性氧的作用。在酸性介质中,染料仅在 10 分钟内就被完全降解,空穴是降解 RhB 的主要活性物种。合成的材料非常稳定,可多次使用而不会明显降低光催化活性。
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引用次数: 0
Theoretical Study on the Synthesis of Urea by Electrochemical Nitrate and Carbon Dioxide over COF Series Catalysts 在 COF 系列催化剂上通过电化学硝酸盐和二氧化碳合成尿素的理论研究
IF 2.1 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2023-10-31 DOI: 10.1007/s10563-023-09408-9
Yingjun Hou, Ling Guo

Catalytic synthesis of urea is a bright substitutable to Haber–Bosch progression and industrial urea synthesis. Electrochemical C–N coupling of carbon dioxide and nitrogen oxides under environmental conditions is a newly developed method, which also provides a novel opinion for solving nitrate contamination. Conjugated organic frameworks (COFs) have been used as prospective electrocatalysts for nitrogen reduction reactions and carbon dioxide reduction reactions (CO2RR) as a result of their regulate structure and multihole properties, resulting in efficient electron transfer. This paper reports the efficient synthesis of urea from carbon dioxide and nitrate over MoM1S-Pc-M2PPs COF (M as a transition metal) electrocatalyst. According to the calculation of DFT, it was found that it was difficult for carbon dioxide and nitrogen oxide to coadsorb on MoM1S-Pc to synthesize urea, so we chose to synthesize CO on the metal porphyrin (M2PPs) structural unit, and then overflow on the bimetallic phthalocyanine and nitrogen oxide to synthesize urea. The possibility of nitrate adsorption on different catalysts was verified by calculation. We screened the stability, nitrate adsorption strength, and catalytic activity of MoM1S-Pc candidates, and the results showed that the most promising candidate catalyst was MoFeS-Pc. At the same time, the CO2RR M2PPs substrate was also screened, and the VPPs structure was selected as the best. In the study of coupling between different nitrogen-containing intermediates and *CO, the C–N coupling mechanism shows that *NOH and *CO are two possible C–N coupling nitrogen intermediates, which are shown to be thermodynamically spontaneous and have an inferior activation barrier. This study not only provisions novel perceptions into urea synthesis by coupling nitrogen oxides with carbon dioxide under environmental conditions, but also paves the way for boosting the sustainable production of carbon and nitrogen-coupled products.

催化合成尿素是哈伯-博什法和工业尿素合成法的一种有效替代方法。二氧化碳和氮氧化物在环境条件下的电化学 C-N 偶联是一种新开发的方法,它也为解决硝酸盐污染问题提供了新的思路。共轭有机框架(COFs)因其规整的结构和多孔特性,可实现高效的电子转移,已被用作氮还原反应和二氧化碳还原反应(CO2RR)的前瞻性电催化剂。本文报道了在 MoM1S-Pc-M2PPs COF(M 为过渡金属)电催化剂上以二氧化碳和硝酸盐为原料高效合成尿素的过程。根据 DFT 计算发现,二氧化碳和氧化氮很难共吸附在 MoM1S-Pc 上合成尿素,因此我们选择在金属卟啉(M2PPs)结构单元上合成 CO,然后在双金属酞菁和氧化氮上溢流合成尿素。通过计算验证了硝酸盐在不同催化剂上吸附的可能性。我们对 MoM1S-Pc 候选催化剂的稳定性、硝酸盐吸附强度和催化活性进行了筛选,结果表明最有前途的候选催化剂是 MoFeS-Pc。同时,我们还对 CO2RR M2PPs 衬底进行了筛选,并选出了最佳的 VPPs 结构。在不同含氮中间体与*CO的耦合研究中,C-N耦合机理表明*NOH和*CO是两种可能的C-N耦合含氮中间体,它们在热力学上是自发的,具有较低的活化势垒。这项研究不仅为环境条件下氮氧化物与二氧化碳偶联合成尿素提供了新的认识,而且为促进碳氮偶联产物的可持续生产铺平了道路。
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引用次数: 0
Polyacrylamide Supported Reagents and Catalysts in Various Organic Reactions 各种有机反应中的聚丙烯酰胺支撑试剂和催化剂
IF 2.1 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2023-10-23 DOI: 10.1007/s10563-023-09407-w
Soheila Ghasemi, Hadieh Rahbar Kafshboran

Functional polymers as solid-supported reagents and catalysts for organic synthesis were conventionally based on cross-linked polystyrene (PS). Polyacrylamide (PAM), modified PAM and their copolymers as hydrophilic support, alternatively can be used as heterogeneous systems in several areas of chemistry and industry. After Regen’s report in 1979 that applied cross-linked PAM as a solid phase cosolvent, PAM-supported reagents and catalysts manifest an excessively important function in various organic reactions. This review summarizes the entire features of PAM and its modified forms and focuses on their most recent and relevant applications in organic transformations. Oxidation–reduction reactions, C–C cross-coupling reactions, and Michael addition reactions are among the most important transformation in which PAM and its derivatives have been widely used. Other reactions like substitution reactions, H2O2 decomposition, 1,3-thiazoles synthesis, oxidative esterification, dichlorocyclopropanation, protection of carbonyl compounds, ring opening of epoxides, and dye decolorization have also been investigated. Furthermore, the efficiency, reusability, and limitations associated with these supported systems are discussed.

Graphical Abstract

Herein, applications of functional polymers based on polyacrylamide, modified PAM and their copolymers for the production of polymer supported reagents and catalysts are reviewed. This review summarizes the entire features of PAM and its modified forms and focuses on their most recent and relevant applications in organic transformations such as oxidation–reduction reactions, C–C cross-coupling reactions, Michael addition reactions etc. Furthermore, the efficiency, reusability, and limitations associated with these supported systems are discussed.

功能聚合物作为有机合成的固体支撑试剂和催化剂,传统上以交联聚苯乙烯(PS)为基础。聚丙烯酰胺 (PAM)、改性 PAM 及其共聚物作为亲水性载体,也可在化学和工业的多个领域用作异构系统。1979 年,Regen 报告称交联 PAM 可用作固相助溶剂,此后,PAM 支持的试剂和催化剂在各种有机反应中发挥了极其重要的作用。本综述总结了 PAM 及其改性形式的全部特点,并重点介绍了它们在有机转化中最新的相关应用。氧化还原反应、C-C 交叉偶联反应和迈克尔加成反应是 PAM 及其衍生物被广泛应用的最重要的转化反应。其他反应,如取代反应、H2O2 分解、1,3-噻唑合成、氧化酯化、二氯环丙烷化、羰基化合物保护、环氧化物开环和染料脱色等,也都得到了研究。本文综述了基于聚丙烯酰胺、改性 PAM 及其共聚物的功能聚合物在聚合物支撑试剂和催化剂生产中的应用。本综述总结了聚丙烯酰胺及其改性形式的全部特点,并重点介绍了它们在氧化还原反应、C-C 交叉偶联反应、迈克尔加成反应等有机转化中的最新相关应用。此外,还讨论了与这些支持系统相关的效率、可重用性和局限性。
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引用次数: 0
Hydrodeoxygenation of Vapor Anisole over Nickel/Cobalt and Alumina/Zeolite Supported Catalysts 气态苯甲醚在镍/钴和氧化铝/沸石载体催化剂上的加氢脱氧反应
IF 2.1 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2023-10-04 DOI: 10.1007/s10563-023-09409-8
Ahmad Yaghi, Labeeb Ali, Toyin Shittu, Mohamed S. Kuttiyathil, Abbas Khaleel, Mohammednoor Altarawneh

Anisole (methoxybenzene) often serves as a potent biomass model compound in hydrodeoxygenation (HDO) reactions with the primary aim to underpin conditions and operations that facilitate conversion of bio-oil into non-oxygenated fuel. However, the majority of studies in literature has focused on its HDO in a solvent environment under excessive conditions of high hydrogen flow rate and elevated pressures. Herein, we investigate HDO of an evaporated stream anisole on a continues flow reactor over four combination of Ni/Co catalysts supported on Zeolite or Al2O3. Catalysts were characterized by various methods which span XRD, SEM-EDS and TPR. The reaction was carried out between 300–600 °C. The highest conversion at 87% was acquired using the Ni–Co/Zeolite catalyst (87%) while producing high yield of phenols and cresols. Synergistic effects brought by the incorporation of Co in the lattice of the catalyst has been discussed. Overall, we obtained a viable HDO path for this biomass model compound using combination of different supported catalysts at moderate operational conditions (relatively intermediate temperatures, ambient pressure, and low H2/Feed ratio).

Graphical Abstract

苯甲醚(甲氧基苯)通常是加氢脱氧(HDO)反应中一种有效的生物质模型化合物,其主要目的是支持将生物油转化为非加氢燃料的条件和操作。然而,文献中的大多数研究都集中在高氢气流速和高压条件下的溶剂环境中的 HDO。在此,我们研究了蒸发流苯甲醚在持续流动反应器中通过沸石或 Al2O3 上支撑的四种 Ni/Co 催化剂组合进行 HDO 的情况。催化剂的表征方法多种多样,包括 XRD、SEM-EDS 和 TPR。反应在 300-600 °C 之间进行。镍钴/沸石催化剂的转化率最高,达到 87%,同时还产生了大量苯酚和甲酚。我们还讨论了催化剂晶格中加入 Co 带来的协同效应。总之,我们在中等操作条件(相对中等的温度、环境压力和较低的 H2/进料比)下使用不同的支撑催化剂组合,为这种生物质模型化合物获得了可行的 HDO 途径。
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引用次数: 0
Hydrogenation of Phenol to Cyclohexanone in Aqueous Phase on WO3 Modified Ni/ZrO2 Catalyst WO3改性Ni/ZrO2催化剂上苯酚水相加氢制环己酮
IF 3 4区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2023-09-07 DOI: 10.1007/s10563-023-09405-y
Yujun Han, Yinteng Shi, Dandan Wang, Hantao Zhou, Jixiang Chen

Ni/ZrO2 (Ni/Zr) and Ni/WO3-ZrO2 (Ni/xWZr, x denotes WO3/ZrO2 mass ratios) were prepared by the impregnation-direct reduction method and tested for the aqueous phase hydrogenation of phenol to cyclohexanone in an autoclave reactor. It has been found that the Ni-W alloy forms in Ni/xWZr, and a charge transfer occurs from Ni to W. The presence of W species promotes the Ni dispersion and increases the amounts of acid sites and spilt-over hydrogen species. This leads to higher hydrogenation and direct deoxygenation activity of Ni/xWZr than that of Ni/Zr. In addition, the W6+ and W4+ species, acted as Lewis acidic sites, may stabilize cyclohexanone and the hydrogenation of cyclohexanone to cyclohexanol is inhibited. Under suitable condition, the phenol conversion and the cyclohexanone selectivity reach 93.1 and 90.6% on Ni/0.8WZr, respectively.

采用浸渍-直接还原法制备了Ni/ZrO2 (Ni/Zr)和Ni/WO3-ZrO2 (Ni/xWZr, x为WO3/ZrO2质量比),并在高压釜反应器中进行了苯酚水相加氢制环己酮的实验。在Ni/xWZr中形成了Ni-W合金,并发生了从Ni到W的电荷转移,W的存在促进了Ni的分散,增加了酸位和溢出氢的数量。这使得Ni/xWZr的加氢和直接脱氧活性高于Ni/Zr。此外,W6+和W4+作为Lewis酸位点,可以稳定环己酮,抑制环己酮加氢生成环己醇。在合适的条件下,在Ni/0.8WZr上苯酚转化率和环己酮选择性分别达到93.1和90.6%。
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引用次数: 0
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Catalysis Surveys from Asia
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