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CATALYSIS SURVEYS FROM ASIA · 2018 ·Vol. 22 ·期 4 ·222-229 · IF 3.081

Conversion of Ethanol and Acetaldehyde to 1, 3-Butadiene Catalyzed by Zr–Si Materials

Gao Meixiang,Jiang Haoxi,Zhang Minhua

Series of ZrO 2 supported on the different kinds of SiO 2 carriers were applied in the reaction of 1, 3-butadiene formation from ethanol and acetaldehyde. ZrO 2 /Nano-SiO 2 performed the best performance with the 1, 3-butadiene selectivity 91.43% and the total conversation 52.39%. Prepared catalysts were characterized by N 2 adsorption–desorption, TEM, XRD, temperature-programmed desorption of NH 3 and CO 2 , FTIR spectroscopy of adsorbed pyridine and CO 2 , Raman XPS. The results show that the weak Lewis acid and basic sites are appropriate for BD formation. Furthermore, more and balance acid-basic sites are rather important for the reaction of ethanol and acetaldehyde conversion to BD.

CAS / MDL: 75-07-0
研究领域: 催化化学 · 材料科学
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FUEL · 2023 · IF 7.4

Enhancement of catalytic activity of PAl-NaX catalyst for side-chain alkylation of toluene with methanol: Effects of dehydrogenation component Cu

Chengda Li,Yueli Wen,Bin Wang,Maohong Fan,Wenlong Liu,Zheng Cui,Wei Huang

Activation and desorption of the hydrogen atom in the toluene methyl is a restrictive step for side-chain alkylation of toluene with methanol (SATM). In this work, two dehydrogenation strategies were used to improve the catalytic performance, dehydrogenation component Cu was introduced in PAl-NaX catalyst as well as the acid-base property was adjusted by changing NaOH loading amount. The relationship among the percentage of acid-base sites, low valence Cu species and the catalytic performances was investigated combined with the multiple characterizations, like X-ray photoelectron spectroscopy (XPS), Temperature-programmed desorption (TPD) of NH 3 and CO 2 , etc. together with ternary regression analysis. It is found that the dehydrogenation component Cu, especially low valence Cu species, promotes the selectivity of side-chain alkylation products to a certain degree, but base sites play an even more critical role in enhancing it.

CAS / MDL: 555-31-7 108-18-9
研究领域: 催化化学 · 材料科学
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MOLECULES · 2023 ·Vol. 28 ·期 15 ·5683 · IF 4.6

Highly Selective and Stable Cu Catalysts Based on Ni–Al Catalytic Systems for Bioethanol Upgrading to n-Butanol

Yan Xiao,Nannan Zhan,Jie Li,Yuan Tan,Yunjie Ding

The catalytic upgrading of ethanol into butanol through the Guerbet coupling reaction has received increasing attention recently due to the sufficient supply of bioethanol and the versatile applications of butanol. In this work, four different supported Cu catalysts, i.e., Cu/Al2O3, Cu/NiO, Cu/Ni3AlOx, and Cu/Ni1AlOx(Ni2+/Al3+molar ratios of 3 and 1), were applied to investigate the catalytic performances for ethanol conversion. From the results, Ni-containing catalysts exhibit better reactivity; Al-containing catalysts exhibit better stability; but in terms of ethanol conversion, butanol selectivity, and catalyst stability, a corporative effect between Ni–Al catalytic systems can be clearly observed. Combined characterizations such as XRD, TEM, XPS, H2-TPR, and CO2/NH3-TPD were applied to analyze the properties of different catalysts. Based on the results, Cu species provide the active sites for ethanol dehydrogenation/hydrogenation, and the support derived from Ni–Al–LDH supplies appropriate acid–base sites for the aldol condensation, contributing to the high butanol selectivity. In addition, catalysts with strong reducibility (i.e., Cu/NiO) may be easily deconstructed during catalysis, leading to fast deactivation of the catalysts in the Guerbet coupling process.Keywords:copper catalyst;hydrotalcite;stability;ethanol;butanol

研究领域: 化学工程 · 催化科学
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Biomass Conversion and Biorefinery · 2022 · IF 4.05

Thermal behaviors and kinetics for cellulose pyrolysis using CexZr1−x-T catalysts

Liu Huiyu,Zhang Jun,Gu Jing,Yuan Haoran,Chen Yong

In the present study, a series of Ce-Zr binary metal oxides (Ce x Zr 1−x -T, x  = 0.2, 0.5, 0.8) with variable physicochemical characteristics were developed for fast pyrolysis of cellulose, wherein thermal decomposition behaviors and kinetics were investigated using TG-MS and Py-GC/MS methods. Comprehensive characterizations including XRD, NH 3 -TPD, CO 2 -TPD, and SEM were conducted to unveil the essential structural properties of as-prepared Ce x Zr 1−x -T materials. Ce x Zr 1−x -T calcined at 450 °C and 550 °C could supply suitable medium to strong acid–base sites and good porosity for the pyrolysis of cellulose into ketones, aldehydes, and hydrocarbons, especially for Ce 0.8 Zr 0.2 –550. Elevation of heating rate and catalyst usage significantly promoted the yielding of ketones, aliphatic hydrocarbons, and aromatic hydrocarbons. Moreover, the activation energy for cellulose pyrolysis was lowered to 96.9 kJ/mol in the presence of Ce 0.8 Zr 0.2 –550, due to the promotional role of existing acid–base sites.

CAS / MDL: 9004-34-6
研究领域: 化学工程 · 能源科学
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APPLIED CATALYSIS A-GENERAL · 2024 · IF 4.7

The synthesis of Ni-Co@NOMC and the regulation of its active sites for the selective conversion of furfural to cyclopentanone

Zhiquan Cai,Zhiyan Zhang,Xuesong Wei,Xiao-Xuan Li,Yi-Si Feng

Catalysts play a critical role in the selective conversion of furfural (FAL) in the aqueous-phase hydrogenation-rearrangement tandem reaction (AP-HRT). Herein, the N-doped bimetallic Ni-Co@NOMC was synthesized by solvent volatilization self-assembly method. The morphology and structure of the APF precursors were effectively controlled through adjustments in the synthesis and the presence of numerous pore channels and the substantial specific surface areas contributed to enhancing catalytic efficiency. Furthermore, this study also examined the synergistic interaction between the acid-base sites of the novel mesoporous N-doped carbon (NOMC) carrier and metal active sites to advance the succession of the furan ring hydrogenation and rearrangement processes. Specifically, the 99.9 % conversion of 8 wt% FAL solution was successfully accomplished with the 90.5 % selectivity of cyclopentanone catalyzed by 1.2-Ni-Co@NOMC catalysts. Therefore, this research holds significant importance for advancing the sustainable utilization of biomass resources in the future.

研究领域: 化学工程 · 催化科学
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ChemSusChem · 2024 ·Vol. 17 ·期 16 ·e202400637 · IF 7.5

Efficient Glucose Isomerization to Fructose using Photoregenerable MgSnO3 Catalyst with Cooperative Acid-Base Sites

Peixin Wang,Wenhua Xue,Jian Ye,Ruilong Zhang,Reeti Kumar,Wenfei Cai,Jun Zhao

Graphical A catalyst for the thermal catalytic reaction of glucose isomerization to fructose that can be regenerated through light illumination. The isomerization of glucose to fructose plays a crucial role in the food industry and the production of biomass-derived chemicals in biorefineries. However, the catalyst used in this reaction suffers from low selectivity and catalyst deactivation due to carbon or by-product deposition. In this study, MgSnO 3 catalyst, synthesized via a facile two-step process involving hydrothermal treatment and calcination, was used for glucose isomerization to fructose. The catalyst demonstrated outstanding catalytic performance, achieving a fructose equilibrium yield of 29.8 % with a selectivity exceeding 90 % under mild conditions owing to its acid-base interaction. Notably, spent catalysts can be regenerated by photoirradiation to remove surface carbon, thereby avoiding the changes in properties and subsequent loss of activity associated with conventional calcination regeneration method. This novel approach eliminates the energy consumption and potential structural aggregation associated with traditional calcination regeneration methods. The acid-base active sites of the catalyst, along with their corresponding catalytic reaction mechanism and photoregeneration mechanism were investigated. This study presents a demonstration of the comprehensive utilization of catalytic material properties, i. e., acid-base and photocatalytic functionalities, for the development of a green and sustainable biomass thermochemical conversion system.

研究领域: 化学工程 · 可再生资源与环境科学
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APPLIED CATALYSIS B-ENVIRONMENTAL · 2020 · IF 16.683

Synergetic mechanism for basic and acid sites of MgMxOy (M = Fe, Mn) double oxides in catalytic ozonation of p-hydroxybenzoic acid and acetic acid

Tongdong Shen,Wentao Su,Qiangqiang Yang,Jun Ni,Shaoping Tong

MgM x O y (M = Fe, Mn) powders prepared by the sol-gel method were used as the catalysts for ozonation of p -hydroxybenzoic acid ( p -HBA) and acetic acid (AcOH) (20 mg/L) at a neutral pH for 9 min. The study aims to bring an insight into the synergetic mechanism for basic and acid sites of MgM x O y in heterogeneous catalytic ozonation. 84.8 %, 88.2 %, 86.7 % p -HBA were removed by ozonation catalyzed by MgFe x O y , MgMn x O y and MgO, respectively. 49.3 %, 65.8 %, 64.3 % AcOH were removed by ozonation catalyzed by the three catalysts, respectively. MgMn x O y exhibited the highest catalytic activity in ozonation of p -HBA and AcOH owing to the action of acid sites of MgMn x O y for additional ozone decomposition. The increase of solution pH, the protonation of surface hydroxyl groups and the electron transfer on acid sites induce ozone decomposition into reactive oxygen species in MgM x O y catalytic ozonation.

研究领域: 环境科学 · 催化化学
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iScience · 2024 · IF 4.6

Zr modulated N doping composites for CO2 conversion into carbonates

Jielin Huang,Jie Wang,Haonan Duan,Li Dong,Songsong Chen,Junping Zhang,Xiangping Zhang

Acidic and basic sites of catalysts are essential for CO 2 capture and activation. In this work, Zr, N-ZnO/ZnAl-LDH-IL composites in ionic liquid and methanol systems were fabricated, and applied to catalyze the synthesis of ethylene carbonate (EC) from ethylene glycol (EG) and CO 2 with about 4.76 mmol EC g Cat. −1 h −1 . The composites showed more strong basic sites due to the effective induction of reactive groups on the catalyst surface by Zr doping, resulting in an increase of pyridinic-N groups from 5.48% to 22.25%. More C atoms adjacent to pyridinic-N as strong basic sites was conducive to the activation of CO 2 and EG. In addition, the possible catalytic pathway and mechanism of the composites for synthesizing EC as well as the doping of La, Fe, Ce, and Cu were also investigated, which provides an effective strategy for regulating the acid-base centers on the catalyst surface through ionic liquids and methanol solvents.

研究领域: 催化化学 · 材料科学
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FUEL · 2020 · IF 5.578

Catalytic hydrothermal liquefaction of microalgae over mesoporous silica-based materials with site-separated acids and bases

Jianwen Lu,Jian Wu,Lilong Zhang,Zhidan Liu,Yulong Wu,Mingde Yang

In this study, four kinds of porous silica-based materials with site-separated acids and bases were prepared, the catalysts possess both micropores and mesopores with a specific surface areas ranging from 764 m 2 /g to 1016 m 2 /g. Moreover, the effects of the catalysts on the yield and quality of bio-oil derived from hydrothermal liquefaction (HTL) of microalgae Chlorella were investigated. The results showed that the catalyst had no obvious change on the bio-oil yield, but they exhibited good performance in the improving of bio-oil quality. Catalyst with acids inside and outside of the pores worked best in denitrification of the bio-oil while catalyst with bases inside and outside of the pores achieved the minimum sulfur content of the bio-oil (0.65%). GC–MS analysis indicated that the catalyst with site-separated acids and bases showed magnified selectivity to hydrocarbons (over 50% of peak area). Furthermore, the catalyst could increase the low boiling fraction (<400 °C) of the bio-oil to from 68% to 81%. At last, the plausible mechanism of catalyst on HTL was proposed. This study could provide valuable information for production of high quality bio-oil in future researches.

研究领域: 能源生物学 · 催化材料科学
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ChemistrySelect · 2024 ·Vol. 9 ·期 31 ·e202400459 · IF 1.9

Hydrogenation of Furfural to Furfuryl Alcohol over PdCu/zirconium Phosphonate with Metal and Lewis Acid Sites

Yongyu Huang,Xinxin Xia,Pei Li,Yaqian Gu,Hua Song,Cuiqin Li,Feng Li

Graphical Hydrogenation of furfural to furfuryl alcohol under H 2 and N 2 atmosphere are studied over PdCu/ZrPO with metal and Lewis acid sites. The PdCu metal active sites of PdCu/ZrPO involve both direct hydrogenation and transfer hydrogenation activities, and the Zr 4+ −O 2− Lewis acid-basic pairs of ZrPO have transfer hydrogenation activity. Hydrogenation of furfural to furfuryl alcohol under H 2 and N 2 atmosphere was studied over zirconium phosphonate (ZrPO)-supported PdCu (PdCu/ZrPO) catalysts. The direct hydrogenation and transfer hydrogenation activities of PdCu metal active sites and the transfer hydrogenation activity of Zr 4+ −O 2− Lewis acid-basic sites were investigated, respectively. The size and the distribution of Cu particles could be adjusted by altering the P/Zr molar ratio. Bimetallic PdCu could enhance the acidity of the PdCu/ZrPO catalysts, and improve the ratio of Lewis/Brønsted acid, which led to an increase in the transfer hydrogenation activity of Lewis acid-basic pairs. The electronic effect between Pd and Cu promoted furfural to absorb onto electron-deficient Cu through η1(O)-aldehyde configuration, which contributed to the direct hydrogenation and the transfer hydrogenation at metal active sites. Especially, the adsorption and dissociation of H 2 in electron-rich Pd were promoted, which significantly improved the direct hydrogenation activity.

研究领域: 催化化学 · 能源化学
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CHEMICAL ENGINEERING SCIENCE · 2020 · IF 3.871

Boron doped magnetic catalysts for selective transfer hydrogenation of furfural into furfuryl alcohol

Danni Li,Jun Zhang,Ying Liu,Haoran Yuan,Yong Chen

A series of boron doped magnetic zirconium catalysts were developed for the selective transfer hydrogenation of biomass-derived furfural (FFR) into furfuryl alcohol (FA) using 2-propanol as hydrogen source and solvent. Full characterizations with XRD, SEM, TG, Py-IR, NH 3 -TPD, and CO 2 -TPD techniques were undertaken to uncover structural properties of magnetic catalysts. Boron doped magnetic zirconium catalysts endowing with adjustable acid-base sites exhibited excellent performance as well as good regenerability in the transfer hydrogenation of FFR, where almost 100% FA yield was achieved in the presence of 2-propanol and the catalyst still sustained good activity after being used five times. Suitable acidity/basicity ratio of 3.8 ~ 4.0 apparently benefited the selective production of FA. Gratifyingly, the activation energy for FA formation over Zr 1 B 3 FeO was as low as 48.3 kJ/mol. In addition, plausible reaction mechanism involving two H-transfer paths for transfer hydrogenation of FFR into FA under the catalysis of active Zr/B species was proposed.

研究领域: 催化化学 · 生物质能 · 材料科学
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CHEMICAL ENGINEERING JOURNAL · 2025 · IF 13.2

Electrocatalytic nitrate-to-ammonia conversion using Mo-S-Fe3O4 nanoplates on foam iron electrode: Synergistic effects of Lewis-acid and Lewis-base sites

Maonan Ran,Guan Zhang

The NO 3 − electroreduction process presents a promising alternative to the Haber-Bosch method by offering dual benefits: removal of nitrates from wastewater coupled with efficient NH 3 production. Herein, Mo and S doped Fe 3 O 4 nanoplates grown on foam Fe (Mo-S-Fe 3 O 4 @FF) with electron-rich Mo δ+ state was synthesized through a facile hydrothermal approach. Notably, Mo-S-Fe 3 O 4 @FF electrode achieved a nearly fourfold enhancement in ammonium yield compared to foam Fe electrode, while also enhancing the NH 3 Faradaic efficiency. At − 1.3 V vs . Ag/AgCl in a K 2 SO 4  + KNO 3 solution, the Mo-S-Fe 3 O 4 @FF electrode attained a NH 3 Faradaic efficiency of 91.3 %. Furthermore, performance was observed to improve with increasing solution pH levels as the reaction proceeded. From both kinetic and thermodynamic perspectives, our findings demonstrate that high NH 3 production activity is characteristic of Mo-S-Fe 3 O 4 @FF—indicating significant enhancements in conversion rates from NO 3 − →NO 2 − →NH 3 . Theoretical calculation, in conjunction with experimental analyses, reveal that the co-modification of Fe 3 O 4 with Mo and S enhances electron transfer capacity during NO 3 − RR. This modification forms Lewis-acid (Fe-Mo) pairs that increase nitrate adsorption energy alongside Lewis-base (S-O) sites that attract protons, thereby improving overall NO 3 − RR activity. This report elucidates the synergistic effects of Lewis-acid and Lewis-base sites on optimizing catalytic performance for NO 3 − RR using foam Fe-based electrodes.

研究领域: 环境科学 · 电催化 · 材料科学
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