CHEMICAL ENGINEERING SCIENCE
·
2025
·
IF 4.3
Zerui Su,Jian Zhang,Yang Li,Zheyu Qiao,Ziyuan Qiao,Lihang Wei,Xiaoyuan Qin,Xiaoxue Mu,Feng-Shou Xiao
Cu-based catalysts are crucial for the dehydrogenation of ethanol (EtOH) to acetaldehyde (AcH); however, their performance decreases at higher temperatures due to the low Tammann temperature of Cu species. In this study, we synthesized silica-supported Cu catalysts using microwave-assisted wet-kneading. Characterization revealed a typical core–shell structure (Cu@SiO 2 -WK), which demonstrated high activity, excellent selectivity, and superior stability for ethanol dehydrogenation. The Cu@SiO 2 -WK achieved 96.2 % EtOH conversion with 99.9 % selectivity to AcH at 260 °C. After 160 h of reaction, it maintained an EtOH conversion of 90.5 % and AcH selectivity of ∼99.9 %. Following simple calcination, the catalyst’s activity was fully regenerated to 96.1 %. Model catalysts and in situ FT-IR spectra indicate that the core–shell structure significantly enhances the catalyst’s performance in the dehydrogenation of EtOH to AcH.
研究领域:
化学工程
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催化科学
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产品关联
DOI
高影响因子
Catalysts
·
2022
·Vol. 12
·期 9
·1049
·
IF 4.501
Yan Hao,Dajie Zhao,Wen Liu,Min Zhang,Yixiao Lou,Zhenzhen Wang,Qinghu Tang,Jinghe Yang
Selective dehydrogenation of ethanol to acetaldehyde has been considered as an important pathway to produce acetaldehyde due to the atom economy and easy separation of acetaldehyde and hydrogen. Copper catalysts have attracted much attention due to the high activity of Cu species in O-H and C-H bonds oxidative cleavage, and low process cost; however, the size of the Cu nanoparticle is difficult to control since it is easily suffers from metal sintering at high temperatures. In this work, the Cu/KIT-6 catalyst exhibited an ultra-high metal dispersion of 62.3% prepared by an electrostatic adsorption method, due to the advantages of the confinement effect of mesoporous nanostructures and the protective effect of ammonia water on Cu nanoparticles. The existence of an oxidation atmosphere had a significant effect on the valence state of copper species and enhancing moderate acid sites. The catalyst treated by reduction and then oxidation possessed a moderate/weak acid site ratio of ~0.42 and a suitable proportion of Cu+/Cu0ratio of ~0.53, which conceivably rendered its superior ethanol conversion of 96.8% and full acetaldehyde selectivity at 250 °C. The catalyst also maintained a high selectivity of >99% to acetaldehyde upon time-on-stream of 288 h.Keywords:copper;ethanol dehydrogenation;mesoporous silica
研究领域:
化学工程
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催化科学
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DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2022
·
IF 24.319
Haolan Liu,Zhili Chang,Jie Fu,Zhaoyin Hou
Cu-based catalysts play pivotal role in many industrial processes, however, its application under high temperature is restricted due to the low Tammann temperature of Cu. Improving the stability and activity of Cu-based catalysts at high temperature is a challenge. In this work, a stable Cu/ZnO@SiO 2 catalyst was prepared, in which silicon was introduced into CuZn-BTC precursor via a steam-assisted hydrolysis method before calcination and reduction. Characterizations found that Cu/ZnO@SiO 2 catalyst prepared via above strategy possesses increased surface area, more exposed active sites and excellent stability for ethanol dehydrogenation than Cu/ZnO (prepared from CuZn-BTC without SiO 2 ). It was confirmed that the space-time yield of acetaldehyde reached 9.0 g-acetaldehyde/g-cat/h, and Cu/ZnO@SiO 2 could maintain its activity within 200 h at 350 °C due to the ZnO decorated Cu particles (Cu/ZnO) were encapsulated in the octahedral shaped SiO 2 hollow.
研究领域:
化学工程
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催化材料科学
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产品关联
DOI
高影响因子
ChemSusChem
·
2022
·Vol. 15
·期 11
·e202200474
·
IF 9.14
Shuai Li,Shenghai Yang,Kangkang Li,Yanqing Lai,Chaoyong Deng,Changhong Wang
Graphical A green system for hafnium alkoxide synthesis was proposed. Simultaneous heterogeneous Hf dissolution and ethanol dehydrogenation followed by spontaneous solution-based binding of alkoxy with Hf 4+ ions gave Hf(OEt) 4 . After the optimum conditions – electrolyte, temperature, current densities, etc. – had been determined, a proof-of-concept experiment achieved waste-free production of Hf(OEt) 4 with high purity and yield. Besides the system‘s green credentials, it showed a high net profit of 30 477 USD per kg Hf(OEt) 4 and could be extended to the synthesis of other hafnium alkoxides. The conventional thermal method of preparing hafnium alkoxides [Hf(OR) 4 , R=alkyl] – excellent precursors for gate-dielectric HfO 2 on semiconductors – is severely hindered by its unsatisfactory environmental and economic burdens. Herein, we propose a promising electrodissolution-coupled Hf(OR) 4 synthesis (EHS) system for green and efficient electrosynthesis of Hf(OR) 4 . The operational principle of the electrically driven system consists of two simultaneous heterogeneous reactions of Hf dissolution and alcohol dehydrogenation, plus a spontaneous solution-based combination reaction. In applying ethanol as solvent and Hf metal as electrodissolution medium, we achieved waste-free production of high-purity hafnium ethoxide [Hf(OEt) 4 ] with an equivalent “a concomitant” reduction in CO 2 emission of 187.33 g CO 2 per kg Hf(OEt) 4 and a high net profit of 30 477 USD per kg Hf(OEt) 4 . This system is very competitive with the thermal process, which unavoidably releases substantial waste and CO 2 for a net profit of 27 700 USD per kg Hf(OEt) 4 . We anticipate that the environmental and economic benefits of the EHS process could pave the way for its practical application.
研究领域:
材料科学
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化学工程
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产品关联
DOI
PubMed
高影响因子
ACTA PHYSICO-CHIMICA SINICA
·
2025
·
IF 13.5
Lele Feng,Xueying Bai,Jifeng Pang,Hongchen Cao,Xiaoyan Liu,Wenhao Luo,Xiaofeng Yang,Pengfei Wu,Mingyuan Zheng
Ethanol dehydrogenation is a vital elementary step in ethanol upgrading, for which Cu-based alloy catalysts are the most promising candidates. Nevertheless, elucidating the underlying reasons for the synergistic effect between alloying components and host metals remains challenging due to the intrinsic structural complexity and dynamic evolution of alloy catalysts under operational conditions. Herein, single-atom Pd modified Cu-MFI catalysts with well-defined structures were designed for ethanol dehydrogenation to acetaldehyde and hydrogen. Comprehensive characterizations using aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (AC-HAADF-STEM), X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations revealed that Pd atoms are isolated by surrounding Cu atoms with a coordination number of 9–10, forming −0.36 e charged single-atom sites and being uniformly dispersed on the surface of Cu catalysts. The newly generated Pd δ − and Cu δ + sites synergistically reduced the activation energy barrier for C–H bond cleavage in ethanol. These sites simultaneously enhanced hydrogen adsorption and H–H bond coupling, leading to improved ethanol conversion and acetaldehyde productivity over Pt/Cu-MFI catalysts.
研究领域:
催化化学
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材料科学
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表面科学
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产品关联
DOI
高影响因子
Catalysis Science & Technology
·
2019
·Vol. 10
·期 1
·70-78
·
IF 5.726
Zeyu Yang,Hengwei Fu,Wenjie Ye,Youyu Xie,Qinghai Liu,Hualei Wang,Dongzhi Wei
Alcohol dehydrogenases (ADHs) together with the economical substrate-coupled cofactor regeneration system play a pivotal role in the asymmetric synthesis of chiral alcohols; however, severe challenges concerning the poor tolerance of enzymes to 2-propanol and the adverse effects of the by-product, acetone, limit its applications, causing this strategy to lapse. Herein, a novel ADH gene smadh2 was identified from Stenotrophomonas maltophilia by traditional genome mining technology. The gene was cloned into Escherichia coli cells and then expressed to yield SmADH2. SmADH2 has a broad substrate spectrum and exhibits excellent tolerance and superb activity to 2-propanol even at 10.5 M (80%, v/v) concentration. Moreover, a new thermostatic bubble column reactor (TBCR) system is successfully designed to alleviate the inhibition of the by-product acetone by gas flow and continuously supplement 2-propanol. The organic waste can be simultaneously recovered for the purpose of green synthesis. In the sustainable system, structurally diverse chiral alcohols are synthesised at a high substrate loading (>150 g L−1) without adding external coenzymes. Among these, about 780 g L−1 (6 M) ethyl acetoacetate is completely converted into ethyl (R)-3-hydroxybutyrate in only 2.5 h with 99.9% ee and 7488 g L−1 d−1 space–time yield. Molecular dynamics simulation results shed light on the high catalytic activity toward the substrate. Therefore, the high 2-propanol tolerance SmADH2 with the TBCR system proves to be a potent biocatalytic strategy for the synthesis of chiral alcohols on an industrial scale.
研究领域:
生物化学
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工业生物技术
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环境科学
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产品关联
DOI
高影响因子
Foods
·
2024
·Vol. 13
·期 5
·745
·
IF 4.7
Yali Tan,Yulin Wang,Yulin Wang,Yuan Wan,Yu Liang,Qiaocui Liu,Mengya Wei,Tao Hou
The aim of this study was to obtain egg-derived peptides with facilitating alcohol metabolism (EPs) by enzymolysis, to identify their structures, and screen small polypeptides with higher activity by molecular docking. The optimum conditions for preparing EPs with facilitating alcohol metabolism were obtained by a single factor experiment, adding 2% Protamex and performing enzymolysis for 3 h with a liquid–material ratio of 35:1. The dose–response relationship experiment showed that 800 mg/kg·bw EPs played a better role in facilitating alcohol metabolism. EPs contained 40% hydrophobic amino acids (HAA), including 9.24% Leu. Eighty-four peptides were identified by HPLC-MS/MS and four peptides with potential activation of alcohol dehydrogenase were further selected by molecular docking. The tetrapeptide Trp-Ile-Val-Asp (WIVD) with the highest binding energy reached −7.16 kcal/mol. These findings suggest that egg is a good source for the preparation of peptides with facilitating alcohol metabolism activity.
研究领域:
食品科学
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生物化学
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药理学
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DOI
PubMed
高影响因子
TRANSACTIONS OF NONFERROUS METALS SOCIETY OF CHINA
·
2024
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IF 4.7
Shuai LI,Sheng-hai YANG,Yong-ming CHEN,Chao-bo TANG,Yan-qing LAI,Chao-yong DENG,Chang-hong WANG
Electrodissolution-coupled hafnium alkoxide synthesis (EHS) is a promising pathway for efficient electro- synthesis. It employs simultaneous heterogeneous reactions of Hf dissolution and ethanol dehydrogenation, and spontaneous solution-based combination reaction between Hf 4+ cations and alkoxy anions. To elucidate the mechanism and kinetics of EHS process, the electrochemical behaviors of anodic Hf dissolution and cathodic ethanol dehydrogenation were explored through electrochemical measurements, SEM observations, gas chromatography, and micro-kinetics modeling. The results indicated the supporting electrolytes of tetraethylammonium chloride (Et 4 NCl) to be preferable, which facilitated a passive-film-punctured pitting mechanism for Hf dissolution and a two-stage dehydrogenation mechanism. Three indicators related to passive rate, sensitivity towards puncture of the passive film, and pitting rate were extracted to quantify the kinetics of passive puncture and Hf corrosion. Micro-kinetics models were developed to evaluate the Et 4 NCl-based EHS process, which achieved electric energy requirements of 1.53–1.83 kW·h/kg Hf(OC 2 H 5 ) 4 .
研究领域:
材料科学
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电化学工程
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产品关联
DOI
高影响因子
CARBOHYDRATE POLYMERS
·
2014
·
IF 3.916
Qingfang Deng,Xin Zhou,Huaguo Chen
In the present study, enzyme assisted extraction of Fructus Mori polysaccharides ( FMPS ) from F. mori using four kinds of enzymes and three compound enzymes were examined. Research found that glucose oxidase offered a better performance in enhancement of the extraction yields of FMPS , antioxidant and activate alcohol dehydrogenase activities. The glucose oxidase assisted extraction process was further optimized by using response surface method ( RSM ) to obtain maximum yield of crude FMPS . The results showed that optimized extraction conditions were ratio of enzyme amount 0.40%, enzyme treated time 38 min, treated temperature 58 °C and liquid–solid radio 11.0. Under these conditions, the mean experimental value of extraction yield (16.16 ± 0.14%) corresponded well with the predicted values and increased 160% than none enzyme treated ones. Pharmacological verification tests showed that F. mori crude polysaccharides had good antioxidant and activate alcohol dehydrogenase activities in vitro.
研究领域:
生物化学
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药理学
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食品科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ELECTROCHIMICA ACTA
·
2020
·
IF 6.215
Fei Zhang,Xingxing Wu,Jiaojiao Gao,Yimai Chen,Yawen Gui,Ling Zhang,Wei Gan,Qunhui Yuan
Herein, we developed an efficient anode catalyst for alcohol biofuel cell by integrating multi-walled carbon nanotubes (MWCNTs) into an isoreticular metal organic framework derived porous carbon. The derived porous carbon (PC) intercalated by MWCNTs (PC/MWCNTs) serviced as the anode component in catalyzing the electrooxidation of reduced β-Nicotinamide adenine dinucleotide (NADH), enabling catalysis to ethanol electrooxidation by alcohol dehydrogenase with NAD + as both free coenzyme and electron transfer mediators (onset potential, 0.14 V vs. SCE, pH 8.0). Hierarchy of PC/MWCNTs with micro-, meso-, and macropores provides improved immobilization of electroactive enzymes, aids the facile transportations of electrolyte and increases the conductivity and specific surface areas of anode and results in a much higher catalytic current density for NADH (1.17 mA cm −2 for 10 mM NADH, pH 9.0) and alcohol bioanode (maximum steady-state current density, 0.25 ± 0.03 mA cm −2 , pH 8.0) than its singular component analogues (PC and MWCNTs). The high Michaelis-Menten constant (166 ± 16.8 mM) favorites the detection of ethanol at high concentrations. The linear range of ethanol is 10–300 mM, with the sensitivity and detection limit as 24 nA mM −1 and 3 mM. The study applies porous carbon nanomaterials as both electrocatalysts for coenzyme and scaffolds for enzymes, benefiting to feasible constructions of bioelectrodes with notable current densities.
研究领域:
材料科学
·
电化学
·
生物催化
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产品关联
DOI
高影响因子
SENSORS AND ACTUATORS B-CHEMICAL
·
2018
·
IF 5.667
Shuyun Zhu,Cuihua Lei,Jing Sun,Xian-En Zhao,Xiao Wang,Xiaolu Yan,Wei Liu,Hua Wang
In the present study, a novel colorimetric sensing platform was constructed for probing the NAD + /NADH-dependent biocatalytic transformations. Manganese dioxide (MnO 2 ) nanosheets as an oxidase-mimicking nanomaterial could directly oxidize 3,3′,5,5′-tetramethylbenzidine (TMB) into oxTMB without the need of H 2 O 2 . Importantly, it was found that NADH could easily trigger the decomposition of MnO 2 nanosheets, causing the decrease of solution absorbance. This is demonstrated by the enzyme catalysis reactions of two dehydrogenase models, ethanol dehydrogenase (ADH) and lactate dehydrogenase (LDH), where NADH is formed and consumed, respectively, in their physiological enzymatic reactions. A MnO 2 -TMB sensing platform was thereby proposed for the analysis of their catalytic reaction substrates including ethanol and pyruvic acid. The detection limits of ethanol and pyruvic acid can reach 5.0 μM and 100 nM, respectively. The developed optical biosensing platform can be used to develop other dehydrogenase-based biosensors followed by monitoring their substrates.
研究领域:
生物化学
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纳米生物学
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分析化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY
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2020
·
IF 4.192
Tian Li,Guo-Song Liu,Wei Zhou,Min Jiang,Yu-Hong Ren,Xin-Yi Tao,Min Liu,Ming Zhao,Feng-Qing Wang,Bei Gao,Dong-Zhi Wei
Squalene has wide applications in the food and pharmaceutical industries. Engineering microbes to produce squalene is a promising alternative for traditional production approaches. In this study, squalene production was enhanced to 978.24 mg/L through stepwise overexpression of the enzymes that catalyze acetyl-CoA to squalene. Subsequently, to increase the activity of HMG-CoA reductase and alleviate the high dependence on NADPH, the HMG-CoA reductase (NADH-HMGR) from Silicibacter pomeroyi, highly specific for NADH, was introduced, which increased squalene production to 1086.31 mg/L. Native ethanol dehydrogenase ADH2 and acetaldehyde dehydrogenase ADA from Dickeya zeae were further overexpressed, which enhanced the capability to utilize ethanol for squalene synthesis and endowed the engineered strain with greater adaptability to high ethanol concentrations. Finally, a remarkable squalene production of 9472 mg/L was obtained from ethanol via carbon source-controlled fed-batch fermentation. This study will greatly accelerate the process of developing microbial cell factories for squalene production.
研究领域:
生物技术
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代谢工程
·
微生物生物技术
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）