Catalysts
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2023
·Vol. 13
·期 7
·1038
·
IF 3.9
Jincheng Wu,Guoguo Liu,Qin Liu,Yajing Zhang,Fu Ding,Kangjun Wang
The hydrogenation of methyl formate to methanol is considered one of the most effective methods for recycling methyl formate products. We recently developed a highly efficient and cost-effective Cu-SiO2catalyst using the ammonia-evaporation (AE) method. The Cu-SiO2-AE catalyst demonstrated superior performance, achieving a methyl formate conversion of 94.2% and a methanol selectivity of 99.9% in the liquid product. The catalyst also displayed excellent stability over a durability test of 250 h. Compared to the commonly used Cu-Cr catalyst in the industry, the Cu-SiO2-AE catalyst exhibited higher conversion of methyl formate and methanol yield under the same reaction conditions. Characterization results revealed a significant presence of Si-OH groups in the Cu-SiO2-AE catalyst. These groups enhanced the hydrogen spillover effect and improved hydrogenation efficiency by preventing sintering during the reaction to stabilize the Cu species. The strategy employed in this study is applicable to the rational design of highly efficient catalysts for industrial applications.Keywords:Cu-SiO2catalyst;hydrogenation of methyl formate;methanol;catalyst stability
研究领域:
化学工程
·
催化化学
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产品关联
DOI
高影响因子
Catalysts
·
2023
·Vol. 13
·期 6
·971
·
IF 3.9
Chunjie Shi,Xiaofeng Yu,Wei Wang,Haibing Wu,Ai Zhang,Shengjin Liu
The catalytic activity and cyclic catalysis of different methyl benzoates were studied by using a series of Lewis solid acid catalysts. The iron-supported zirconium/titanium solid acid catalysts were characterized using FTIR, SEM, XRD, and BET. The details of catalytic activity and cyclic catalysis verified that the catalyst catalyzed the reactions of 31 benzoic acids with different substituents and methanol. In addition, the mechanism was revealed according to the microstructure, acid strength, and specific surface area of the catalysts, and the yields of methyl benzoates by the GC-MS. Zr ions had significant effects on the catalytic activity of the catalyst. A certain proportion of Fe and Ti ions additionally enhanced the catalytic activity of the catalyst, with the catalyst-specific composition of Fe:Zr:Ti = 2:1:1 showing optimal catalytic activity. A variety of substituents in the benzene ring, such as the electron-withdrawing group, the electron-donating group, large steric hindrance, and the position of the group on the benzene ring, had regular effects on the catalytic activity of the methyl benzoates. An increase in the catalyst activity occurred owing to the increases in the catalyst surface and the number of acid sites after the Fe ion was added. The catalytic activity remained unchanged after the facile recycling method was performed.Keywords:zirconium/titanium solid acid;iron-supported;methyl benzoate compounds
研究领域:
催化化学
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材料科学
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DOI
高影响因子
JOURNAL OF CHEMICAL AND ENGINEERING DATA
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2012
·
IF 1.693
Baimei Yang,Hui Wan,Guofeng Guan
Isobaric vapor–liquid equilibrium (VLE) data are reported for binary mixtures of methyl formate + o-xylene, methyl formate + m-xylene, methyl formate + p-xylene, and methyl formate + ethylbenzene at 101.33 kPa. The data are obtained using a vapor recirculating type (modified Othmer's) equilibrium still. All of the binary systems show positive deviation from ideality. None of the systems form an azeotrope. The VLE data for these binary systems are checked to meet rigorous thermodynamic consistency by the Herington method and the point-to-point test of the Fredenslund method. The experimental VLE data are well-correlated by the nonrandom two-liquid (NRTL), universal quasichemical activity coefficient (UNIQUAC), and Wilson equations.
研究领域:
化学工程
·
热力学
✓ 已验证
产品关联
DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
·
2021
·
IF 8.271
Jianfang Liu,Zhenzhen Ran,Qiyan Cao,Shengfu Ji
The selective oxidation of methanol to methyl formate is one of the most attractive processes to obtain value-added methanol-downstream products. The development of highly efficient and stable catalysts is critical for this transformation. In this study, a series of MIL-88B(Fe x ,Co 1– x ) bimetallic catalysts with different Fe/Co molar ratios were prepared through a one-pot hydrothermal method. X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, energy dispersive spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, N 2 adsorption-desorption, and inductively coupled plasma-mass spectrometry characterization were performed to elucidate the structure of the catalysts. The activity of the catalysts were assessed in the one-step oxidation of methanol to methyl formate with H 2 O 2 in a liquid-phase batch reactor. The results show that the MIL-88B(Fe x ,Co 1– x ) catalysts exhibit uniform needle-like morphologies with an average length and width of 400–600 nm and 100–150 nm, respectively. Co 2+ is incorporated into the framework by partially replacing Fe 3+ in MIL-88B. Moreover, the catalyst efficiently promoted the conversion of methanol to methyl formate. When MIL-88B(Fe 0.7 ,Co 0.3 ) catalyst was used with a molar ratio of H 2 O 2 to methanol of 0.5 at 80 °C for 60 min, 34.8% methanol conversion was achieved, and the selectivity toward methyl formate was 67.6%. The catalysts also showed great stability with a steady conversion and selectivity even after four cycles. The preliminary oxidation mechanism was also studied. It was determined that H 2 O 2 is first adsorbed on the Fe 3+ sites and subsequently activates these sites. Methanol is adsorbed by the O atoms of the framework through hydrogen bonding and is gradually oxidized to formic acid . Subsequently, formic acid reacts with the residual methanol at the Fe 3+ and Co 2+ Lewis acid sites to form methyl formate.
研究领域:
化学工程
·
催化化学
✓ 已验证
DOI
高影响因子
JOURNAL OF CHEMICAL AND ENGINEERING DATA
·
2012
·
IF 1.693
Li Yanfen,Yuan Pingfang,Ji Jia,Zhou Jianguo,Zhu Rongjiao,Tian Yiling
Vapor–liquid equilibrium data p, T, x, ρ, and Vm at (293.2, 313.2, 333.2, and 353.2) K and pressures between (1.39 and 9.96) MPa for the binary systems of carbon monoxide (CO) + propionic acid (PA) and carbon monoxide + methyl formate (MF) were reported. The equilibria were measured using a variable-volume cylindrical autoclave. The experimental data were modeled using the Peng–Robinson (PR) equation of state (EOS) and Peng–Robinson–Stryjek–Vera (PRSV) equation of state with van der Waals I or Panagiotopoulos–Reid mixing rules. The compared results showed a satisfactory agreement between the correlated and the experimental data. The binary interaction parameters were also obtained. At the same time, the Henry's coefficient, molar solution enthalpy, and molar solution entropy of CO in propionic acid and methyl formate were calculated.
研究领域:
化学工程
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热力学
✓ 已验证
产品关联
DOI
高影响因子
ChemSusChem
·
2024
·
IF 7.5
Ke-An Wang,Zhen-Long Wang,Hai-Bin Zhu
Graphical Efficient electrosynthesis of methyl formate is achieved through the facile reaction between formaldehyde produced from anodic methanol oxidation, and methoxy bromide which is in-situ generated by reaction of Br 2 from anodic oxidation of Br − and methoxide from cathodic methanol reduction. This method features high atomic economy only producing valuable methyl formate and hydrogen gas. Methyl formate (MF) is one of the most important chemical commodities, which has a wide range of applications. Due to environmental friendliness, mild reaction conditions, and easy operations, electrosynthesis of MF has garnered increasing attention in recent years. In this work, we reported an electrosynthesis route toward MF in a halide-containing methanol solution. The thorough mechanistic investigations point out that electrosynthesis of MF is accomplished by instant reaction between aldehyde from anodic methanol oxidation, and methoxy bromide (CH 3 OBr) that is in-situ generated by reaction of Br 2 from anodic oxidation of Br − with methoxide (CH 3 O − ) from cathodic reduction of methanol. This method features high atomic economy only producing valuable MF and hydrogen gas, and shows distinct advantages compared to the reported MF electrosynthesis methods. Even at 200 mA/cm 2 , the faradaic efficiency (FE) of MF remains consistently around 60 % at the anode while a 100 % FE hydrogen gas is produced at the cathode.
研究领域:
化学工程
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电化学
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绿色化学
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产品关联
DOI
PubMed
高影响因子
CHINESE JOURNAL OF CATALYSIS
·
2018
·
IF 3.525
Yu Zhang,Chenliang Ye,Cuili Guo,Changna Gan,Xinmeng Tong
A series of indium oxide-modified Cu/SiO 2 catalysts were synthesized and used to produce ethanol via methyl acetate hydrogenation. In-Cu/SiO 2 catalyst containing 1.0 wt% In 2 O 3 exhibited the best catalytic activity and stability. The physicochemical properties of the synthesized catalysts were investigated using several characterization methods and the results showed that introducing suitable indium to Cu/SiO 2 increased the copper dispersion, diminished the copper crystallite size, and enriched the surface Cu + concentration. Furthermore, the Cu/SiO 2 catalyst gradually deactivated during the stability test, which was mainly attributed to copper sintering and the valence change in surface copper species. In contrast, indium addition can inhibit the thermal transmigration and accumulation of copper nanoparticles to stabilize the catalyst.
研究领域:
催化化学
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材料科学
✓ 已验证
DOI
高影响因子
FUEL
·
2023
·
IF 7.4
Yuting Jin,Yanhong Quan,Yan Li,Jinxian Zhao,Jun Ren
A series of chainlike ZSM-5 supported Cu catalysts with the addition of citric acid (CA) was conveniently prepared using a complexation-impregnation method and employed in the methanol dehydrogenation to methyl formate (MF). The catalytic performance of Cu x /CZ5 first increased and then decreased with increasing CA/Cu ratio, reached 35.0% methanol conversion and 88.3% MF selectivity for Cu1.8/CZ5, significantly higher than that of Cu/CZ5. The superior catalytic performance might be principally explained by the higher Cu 0 concentration combined with abundant Brønsted acid sites, which are responsible for methanol conversion and MF selectivity, respectively. This work provides new insights into the synergy between Cu 0 species and surface acidity of Cu x /CZ5 catalysts for methanol dehydrogenation and offers a feasible and effective strategy for enhancement of the catalytic performance of copper-based catalysts.
研究领域:
催化化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS
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2021
·
IF 5.541
Xin Zhong,Hu Wang,Qingming Zuo,Zunqing Zheng,Jinglan Wang,Wenhao Yin,Mingfa Yao
Polyoxymethylene dimethyl ethers (DMM n ) is regarded as a potential alternative fuel for transportation utilization. The jet stirred reactor (JSR) pyrolysis of DMM 1−3 was studied at temperatures of 450∼1080 K and pressures of 1.03 atm with the residence time (τ) of 2 s. A gas chromatography/mass spectrometry (GC–MS/FID) was used to detect and provide reliable pyrolysis experimental data. Seven key pyrolysis products were detected and measured in the present work, including fuel, methyl formate, methanol, acetaldehyde, methane, ethane and ethylene. A detailed kinetic model of DMM 1−3 pyrolysis was elaborated. Both rate of production (ROP) and sensitivity analysis were performed to reveal the DMM 1−3 pyrolysis processes. Results show that the chemical kinetic simulation can reproduce the consumption of fuel and most intermediate species reasonably well. With the increase of n from 1 to 3 inside DMM 1−3 , the reactivity increases evidently and the initial pyrolysis temperature decreases significantly, which is mainly resulted from different fuel-specific chain initiation reactions of DMM 1−3 . Methane and methyl formate are two detected key species with relatively significant concentrations. It was revealed that the fuel-specific chain initiation reactions of DMM 1−3 can also significantly affect the production and consumption paths of methyl formate. In addition to the major production and consumption paths of formaldehyde, two key competitive channels were found to perform relatively high negative sensitivity to formaldehyde production of DMM 2 and DMM 3 .
研究领域:
化学工程
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能源科学
✓ 已验证
DOI
高影响因子
FUEL
·
2025
·
IF 7.5
Yan Li,Jinxian Zhao,Aolue Yan,Yanhong Quan,Jun Ren
In the methanol dehydrogenation to methyl formate (MF), it is of primary importance to improve the selectivity toward MF through inhibiting decomposition of methanol to CO and H 2 . Herein, the copper catalysts supported on hierarchical hollow silica spherical (HHSS) were synthesized by the ammonia assisted deposition precipitation (ADP) method and tested in the reaction. The 5Cu/HHSS catalyst exhibits the superior activity with a turnover frequency (TOF MF ) value, while 10Cu/HHSS shows the optimal MF selectivity of 98.1 %. It is found that there is a positive correlation between TOF MF and Cu dispersion, as well as between MF selectivity and Cu 0 concentration. Thanks to the unique structure of HHSS with large cavities and abundant mesopores, the ADP method can facilitate a high dispersion of copper on silica and promotes the formation of more active Cu 0 sites, which therefore results in superior activity and MF selectivity of the Cu/HHSS catalysts in the methanol dehydrogenation to MF.
研究领域:
催化化学
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材料科学
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产品关联
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2018
·
IF 4.439
Halidan Maimaiti,Abuduheiremu Awati,Gunisakezi Yisilamu,Dedong Zhang,Shixin Wang
For decades, researchers have been looking for a high-efficiency, low-cost, and environment-friendly photocatalyst for CO 2 reduction. In this work, we employed SOCl 2 chlorination and EDA passivation to decorate the surface of nanocellulose crystals (NCC), and obtained aminated cellulose crystal NCC-EDA. Next, using coordination and dispersion of amino, hydroxyl, and other functional groups at the NCC-EDA surface, the TiO 2 nanoparticles synthesized in-situ from Ti(OBu) 4 were coated by NCC-EDA via a hydrothermal synthesis approach. Subsequently, the composite photocatalyst TiO 2 /NCC-EDA with various NCC-EDA contents was fabricated. The structure, optical properties, and photocatalytic CO 2 reduction performance of the photocatalyst were measured. The results suggest that the NCC-EDA based composite catalyst has highly efficient electron-hole separation and electron transfer as well as excellent CO 2 adsorption ability. The TiO 2 /NCC-EDA exhibits outstanding photocatalytic CO 2 to HCOOCH 3 conversion performance. At reaction time of 6 h, the HCOOCH 3 yield is 372.85 µmol/g cat, which is 4.5 times the yield of pure TiO 2 photocatalyst.
研究领域:
材料科学
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环境科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
ChemElectroChem
·
2023
·Vol. 10
·期 18
·e202300255
·
IF 4
Jia Shen,Yating Zhu,Fengmei Zhou,Luyu Wang,Manli Guo,Yujuan Cao
Graphical Phosphorus-doped porous carbon coated graphite felt (P-GF) : It exhibited excellent hydrophilicity and infiltrating property, and it enhanced electrochemical reduction of O 2 and could significantly enhance the yield of H 2 O 2 . About 98.5 % of methylparaben could be degraded within 180 min, and four parabens could be simultaneously removed. The P-GF exhibited outstanding reusability. Pharmaceuticals and personal care products (PPCPs) are currently drawing significant attention due to their environmental impact. Electro-Fenton, one of the advanced oxidation processes (AOPs), is an efficient and comprehensive technology to degrade all kinds of organic pollutants, but the degradation efficiency relies on cathode material. In this work, phosphorus-doped porous carbon material coated graphite felt (P-GF) was prepared by adopting phytic acid as a phosphorus source through high temperature solid-state method. The microstructure and the elements composition of this fabricated material were investigated by SEM, BET and XPS. With phosphorus doping and plenty of carbon porous structures, the hydrophilicity and infiltrating property of the P-GF had been greatly improved. The prepared P-GF material enhanced the electrochemical reduction of O 2 and could significantly enhance the yield of H 2 O 2 . It was used as a cathode to degrade pollutants under a constant potential, and methylparaben (MePa) was chosen as a research model for optimizing the experimental conditions and analyzing the possible degradation pathway. The P-GF cathode achieved an excellent ability of degrading nearly 100 % of methylparaben within 3 h. The simultaneous removal ability of the P-GF to four parabens was impressed. Additionally, the P-GF material exhibited outstanding reusability.
研究领域:
环境科学
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材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
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