FUEL
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2025
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IF 7.5
Zhangkai Qian,Jia-qi Bai,Mei Ma,Huangfei Liu,Mengdie Cai,Jingshuai Chen,Song Sun
N -methylation of amines, nitro compounds and nitriles with CO 2 and H 2 offers a promising strategy for CO 2 utilization. However, developing highly efficient and stable Cu-based catalysts for selective mono- N -methylation of aniline remains challenging. Herein, we report the successful synthesis of a Cu-ZnO/TiO 2 catalyst, with the optimized 5 %Cu-7.5 %ZnO/TiO 2 catalyst achieving a 96.7 % yield of N -methylaniline (MA) and an initial turnover frequency (TOF) of 7.4 h −1 after 6 h under 453 K, 2 MPa CO 2 and 4 MPa H 2 . This performance surpasses all reported Cu-based catalysts and rivals noble metal-based systems. The catalyst demonstrated reusability at least four cycles and versatility in the N -methylation of various amines, nitro compounds, and nitriles. Kinetic studies revealed reaction orders of 0 with respect to aniline concentration and CO 2 pressure, and 1 with respect to H 2 pressure. Based on kinetics and extensive characterization, we propose a reaction mechanism over 5 %Cu-7.5 %ZnO/TiO 2 , identifying Cu nanoparticles as the active sites. The process proceeds via N -phenylcarbamic acid and N -phenylformamide intermediates, with the hydrogenation of N -phenylcarbamic acid as the rate-determining step.
研究领域:
化学工程
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催化科学
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环境科学
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DOI
高影响因子
JOURNAL OF MEMBRANE SCIENCE
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2021
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IF 8.742
Yilin Wang,Senqing Fan,Zeyi Xiao,Zenghui Mai,Ke Bai,Jiaojiao Chen,Yu Chen,Jingyun Liu
A catalytic membrane nano reactor (CMNR) with deep-permeation nanocomposite structure (DPNS) has been fabricated by flowing synthesis for methanol dehydrogenation to formaldehyde. In this structure, Cu/ZnO nanoparticles are in situ immobilized in the pores of Ti membrane substrate with thickness 1 mm, pore size 10 μm and porosity 45%. The characterization by XRD , TGA , XPS, SEM and TEM indicates that the Cu/ZnO nanoparticles with mean size of 82 nm was successfully embedded into the membrane pores, and well distributed along the thickness direction of the membrane. The ICP measurement results demonstrate that the immobilization amount of 20 mg of Cu/ZnO nanoparticles per gram of Ti membrane substrate can be obtained. The prepared Cu/ZnO/Ti CMNR was built in the technological apparatus for catalytic dehydrogenation of methanol. For one sheet of membrane setting up, the conversion efficiency of methanol 7.5%, the mass specific activity 183 mmol MeOH ·h -1 ·g cat -1 , the pressure drop 2.7 kPa with gas permeating the membrane have been measured, under mass ratio of Cu to ZnO 0.05 in the membrane, reaction temperature 360 °C, the gas flux 8 m 3 ·m -2 ·h -1 through the membrane. The selectivity of formaldehyde is up to 98% and increases with increasing reaction temperature, the highest mass specific activity of 318 mmol MeOH ·h -1 ·g cat -1 can be achieved with mass ratio of Cu to ZnO 0.12 at 360 °C. For three sheets of CMNRs setting up in serials, over 18% of conversion efficiency has been achieved with gas pressure drop 6.8 kPa. If 70 sheets of CMNRs are packed in serials to build a reactor with 70 mm thickness, which will produce the gas pressure drop 162 kPa, the conversion efficiency of 99% would be expected according to a simple simulation based on the experimental measurement.
研究领域:
化学工程
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材料科学
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催化技术
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DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2024
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IF 13.3
Yanhu Han,Zhaowei Jia,Wenxue Gong,Xuechun Wei,Yu Zhang,Mengying Tao,Yaofei Ren,Zuyi Lu,Yutong Wu,Jianhua Chen,Zhongfeng Shi,Zhenxia Zhao,Zhongxing Zhao
Developing photocatalysts with high activity and selectivity remains a significant challenge in the field of CO 2 photoreduction for producing valuable chemical or fuel products under mild conditions. Herein, photonic crystal (PC) GDY-Cu/ZnO was constructed through the in-situ induced growth of graphdiyne (GDY) on PC Cu/ZnO surface via H 2 -reduction for efficient photoreduction of CO 2 to CH 4 . With the aid of photonic crystal structure, PC GDY-Cu/ZnO exhibits a distinctive red-edge slow light region which can significantly improve the utilization efficiency of visible light and intensify photo-catalysis. Additionally, the formed all-solid-state Z-scheme system efficiently accelerates photoelectron migration, facilitating e - /h + separation. Thirdly, the surface GDY, along with the enrich oxygen vacancies generated during H 2 reduction, enhances the adsorption and activation toward CO 2 and H 2 O on PC GDY-Cu/ZnO interface. In consequence, PC GDY-Cu/ZnO demonstrates highly photocatalytic conversion of CO 2 to CH 4 , achieving a CH 4 yield of 33.67 μmol·g −1 ·h −1 with 93.3 % selectivity via slow-light-driven photocatalysis CO 2 reduction. This work provides an efficient strategy to modify ZnO for the efficient photoreduction of CO 2 to CH 4 .
研究领域:
材料科学
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环境科学
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化学工程
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光催化
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DOI
高影响因子
ACS Sustainable Chemistry & Engineering
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2020
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IF 7.632
Qian Wang,Zhi Yu,Junting Feng,Paolo Fornasiero,Yufei He,Dianqing Li
The production of biofuel 2,5-dimethylfuran (DMF) from an important biomass platform of 5-hydroxymethyl furfural (HMF) involves a complicated reaction pathway due to the competition of C═O hydrogenation and C–O hydrogenolysis; however, the dependence of formed intermediates and catalytic sites needs to be further identified. Herein, we constructed a highly efficient and selective Cu/ZnO-Al2O3 catalyst via reduction of a CuZnAl-layer double hydroxide (LDH) precursor, aimed for studying the effect of Cu0/Cu+ species on forming different intermediates and their synergetic promotional effect on HMF hydrodeoxygenation. As expected, the dependence of formation of different intermediates on the Cu+/Cu0 ratio was observed; notably, Cu/ZnO-Al2O3 with higher Cu+/Cu0 ratio finally gave 90.1% DMF selectivity at 100% HMF conversion, more selective than CuNi/Al2O3 (59.6%) and Cu/MgO-Al2O3 (75.8%) references. By a combined study of in situ IR experiments, the observed correlation between the reaction intermediates and the Cu0/Cu+ site suggests that Cu0 tends to adsorb the C═O bond as well as hydrogen molecule, while the Cu+ site is preferable to adsorb and activate the C–O bond. With the synergy of dual active sites, the Cu/ZnO-Al2O3 catalyst showed both high activity and selectivity to DMF. This work provides deep insight into the nature of active Cu species in multiple functional group biomass platform transformation.
研究领域:
催化
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化学工程
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生物化学
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材料科学
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产品关联
DOI
高影响因子
Small
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2025
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IF 12.1
Guangrong Qian,Renyuan Deng,Xiangmei Liu,Yi Wang,Jin Huang,Congyang Mao,Chaofeng Wang,Hanpeng Liu,Zhaoyang Li,Shengli Zhu,Hui Jiang,Zhenduo Cui,Yufeng Zheng,Shuilin Wu
The transmission of pathogenic bacteria via the contaminated surfaces of interactive touchscreens is an important route of infection. It is therefore imperative to develop a functional film with antibacterial properties to prevent cross-infection. In this paper, a bilayer thin-film structure composed of iron-doped and copper-doped zinc oxide (Fe-ZnO/Cu-ZnO) is synthesized through a spin coating technique based on sol-gel. The synergistic effects of metal ion doping, combined with the influence of the internal electric potential, during the photocatalytic reaction process, promote the separation and migration of photogenerated carriers. As a result, it notably boosts the photocatalytic properties. The nanofilm is demonstrated to achieve a rapid bactericidal effect (surpassing 90%) under sunlight irradiation. Furthermore, it is shown to completely kill bacteria after 20 min of illumination and to maintain excellent antibacterial performance (surpassing 90%) for a period of 30 days. Concurrently, the thin film displays both exceptional light transmittance (surpassing 90%) and noteworthy benefits, including environmental sustainability, cost-effectiveness, and the capacity for safe disinfection. The thin film exhibits considerable potential for implementation on surfaces subject to high-frequency public contact. It boasts extensive application prospects and serves as a foundational reference for the design of photocatalytic antibacterial thin films.
研究领域:
材料科学
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纳米技术
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光催化
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环境科学
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表面工程
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DOI
PubMed
高影响因子
Catalysis Science & Technology
·
2019
·Vol. 9
·期 10
·2673-2681
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IF 5.726
Bing Hu,Yazhi Yin,Zixin Zhong,Dengdeng Wu,Guoliang Liu,Xinlin Hong
Maximizing the Cu–ZnO interface is regarded as the best strategy to promote methanol synthesis activity over CuZn catalysts. Reducing the ZnO particle size can enhance the Cu–ZnO interaction, but its synthesis with a sub-5 nm size still remains a challenge. Moreover, the fabrication of an active powder catalyst with an inverse ZnO/Cu configuration is still very rare. In this work, we report a facile synthesis of inverse ZnO/Cu catalysts by direct calcination of Cu@ZIF-8 (zeolitic imidazolate framework-8). The particle size of ZnO and Cu can be tuned by changing the Cu loading as well as the calcination temperature. Importantly, inverse ZnO/Cu catalysts with sub-5 nm ZnO were obtained under gentle calcination at 623 K. In the CO2 hydrogenation reaction, the highest methanol synthesis activity reached 933 g kgcat−1 h−1 at 533 K and 4.5 MPa, with a high turnover frequency (TOF) of 0.013 s−1, over an optimized C2Z-623 catalyst, which exceeds the commercial CuZnAl catalyst (HiFuel R120, Johnson Matthey) and has ranked the top reported value over advanced CuZn catalysts under comparable conditions. Such excellent activity is attributed to the inverse structure of Cu particles covered by sub-5 nm ZnO, which promotes the intimate Cu–ZnO interface with enhanced SMSI. Moreover, we find that the methanol turnover frequency (TOF) monotonically increases with decreasing the particle size of ZnO as well as Cu. It is proposed that reducing the ZnO size favors the spillover of reducible ZnOx species onto the Cu surface while lowering the Cu size is responsible for the enhanced amount of exposed Cu steps for accommodating Zn species, both of which could facilitate the formation of Zn covered Cu steps as active sites for methanol synthesis.
研究领域:
化学工程
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催化材料科学
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DOI
高影响因子
Journal of CO2 Utilization
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2019
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IF 5.189
Yuhai Sun,Chunlei Huang,Limin Chen,Yujun Zhang,Mingli Fu,Junliang Wu,Daiqi Ye
Plate-like ZnO, dominantly exposed (002) polar facet, supported Cu catalysts were prepared by impregnation method as model catalysts for CO 2 hydrogenation to methanol under the real reaction conditions. The catalysts were thoroughly characterized by Scanning electron microscope (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), in situ Raman spectra , Temperature-programmed reduction (H 2 -TPR) and CO 2 Temperature-programmed desorption (CO 2 -TPD). Catalyst microstructures can be obviously tuned through the increasing of Cu content, interface constituted by Cu-Plate ZnO direct contact, interface constituted by Cu (on ZnO) covered by migrated ZnO x and interface constituted by isolated Cu nanoparticles covered by migrated ZnO x . These microstructures displayed different catalytic performance for CO 2 hydrogenation to methanol; among them, interface caused by the migrated ZnO x covered Cu nanoparticles should play vital roles for methanol production.
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
Molecular Catalysis
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2026
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IF 4.3
Minghao Geng,Jiahao Li,Zhengze Li,Meng Sui,Fashe Li,Hua Wang,Zhiyu Hua
Fe-modulated Cu-ZnO CeO 2 catalysts were synthesized via sol-gel method. • Moderate Fe doping suppressed CuO growth and improved Cu dispersion. • Fe tuned the interface and oxygen defects to balance reducibility. • Fe10-CZCe achieved 14.5% CO 2 conversion with high methanol selectivity. • The promotion by Fe stems from interfacial regulation, not new phases. Copper-based catalysts have been widely applied in methanol synthesis from CO 2 hydrogenation. Yet efficient operation at an industrially relevant level remains challenging. The use of CO 2 as a carbon source is still limited by difficult molecular activation and by imperfect interfacial matching. Here, a series of Fe-doped Cu-ZnO CeO 2 catalysts was prepared by a sol-gel route. The influence of Fe content on phase structure, surface electronic environment, reduction behaviour, CO 2 adsorption characteristics and catalytic performance was examined systematically. Fe incorporation did not change the fundamental phase composition of CuO and CeO 2 . It did, however, strongly affect Cu dispersion, the near-surface defect environment of CeO 2 , and the electronic structure of the interface. Moderate Fe addition suppressed CuO crystallite growth, improved Cu dispersion, and produced a more concentrated reduction profile with a more suitable distribution of CO 2 adsorption strength. Excess Fe enhanced defect-related signals and high-temperature adsorption, but also increased interfacial perturbation, which was unfavourable for the further conversion of intermediates. At 3 MPa and 260 °C, Fe10-CZCe showed the best overall performance, giving a CO 2 conversion of 14.5% together with high methanol selectivity and the highest methanol space-time yield. The beneficial role of Fe is therefore linked to reconstruction of the Cu-ZnO CeO 2 interface, which promotes a more effective balance between CO 2 adsorption, activation and hydrogenation. These findings provide a useful perspective for compositional tuning and interface design in Cu-based catalysts. Download: Download high-res image (231KB) Download: Download full-size image
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高影响因子
Frontiers in Chemistry
·
2022
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IF 5.545
Arsalan Muhammad,Saddique Imram,Baoji Miao,Awais Azka,Khan Ilyas,Shamseldin Mohamed A.,Mehrez Sadok
We aimed to synthesize sensitive electrochemical sensors for hydrogen peroxide sensing by using zinc oxide nanorods grown on a fluorine-doped tin oxide electrode by using the facial hydrothermal method. It was essential to keep the surface morphology of the material (nanorods structure); due to its large surface area, the concerned material has enhanced detection ability toward the analyte. The work presents a non-enzymatic H2O2 sensor using vertically grown zinc oxide nanorods on the electrode (FTO) surfaces with Cu nanoparticles deposited on zinc oxide nanorods to enhance the activity. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), energy-dispersive X-Ray (EDX), X-ray diffraction (XRD), and electrochemical methods were used to characterize copper–zinc oxide nanorods. In addition to the high surface area, the hexagonal Cu-ZnO nanorods exhibited enhanced electrochemical features of H2O2 oxidation. Nanorods made from Cu-ZnO exhibit highly efficient sensitivity of 3415 μAmM−1cm−2 low detection limits (LODs) of 0.16 μM and extremely wide linear ranges (0.001–11 mM). In addition, copper-zinc oxide nanorods demonstrated decent reproducibility, repeatability, stability, and selectivity after being used for H2O2 sensing in water samples with an RSD value of 3.83%. Cu nanoparticles decorated on ZnO nanorods demonstrate excellent potential for the detection of hydrogen peroxide, providing a new way to prepare hydrogen peroxide detecting devices.
研究领域:
材料科学
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分析化学
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生物医学工程
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DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2015
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IF 2.587
Jie Sun,Shaolong Wan,Fen Wang,Jingdong Lin,Yong Wang
A variety of catalysts for higher alcohol synthesis from syngas have been under development for potential commercial application, which are still facing challenges, including poor carbon efficiency due to low selectivity to desired products. In this contribution, we systematically studied the effects of temperature, loading of K and Cs, space velocity, and CO2 addition on the alkali-promoted Cu/ZnO/Al2O3 catalysts in order to achieve a high yield of desired higher alcohol products. Our particular focus was to maximize the carbon efficiency by restricting the amount of undesired byproducts, such as lower alkanes and CO2 that could be formed. Among K and Cs promoted Cu/ZnO/Al2O3 catalysts studied, Cs-promoted Cu/ZnO/Al2O3 catalysts exhibit better performance to higher alcohols and higher carbon efficiency than K-promoted counterparts under similar conditions studied. 1.64 mol % Cs-promoted Cu/ZnO/Al2O3 catalyst achieves the highest selectivity to higher alcohols (24.9%) at a CO conversion of 41.6% under 290 °C, 1875 mL g–1cat h–1, 5.4 MPa. The presence of a small amount of CO2 of 2.5 mol % in the feed has negligible effect on the productivity of higher alcohols but significantly suppresses the formation of CO2 byproduct. With the further increase of CO2 in the feed, the formation of CO2 can be further suppressed but at the expense of productivity loss of higher alcohols, which is probably due to the neutralization of surface Cs sites. The best carbon efficiency can be achieved at 8% mol CO2 in the feed.
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
CATALYSIS TODAY
·
2023
·
IF 5.3
Hangjie Li,Liang Wang,Feng-Shou Xiao
Cu/ZnO/Al 2 O 3 catalyst has been widely studied in the hydrogenation of CO 2 to methanol, but it still suffers from insufficient catalyst stability and methanol selectivity. Herein, we overcome these issues by introducing the silica promoter to the catalyst, achieving the Cu/ZnO/Al 2 O 3 /SiO 2 (CZAS) catalysts with significantly improved methanol selectivity and catalyst durability. Characterizations of samples showed that the silica species efficiently hindered the sintering of Cu nanoparticles during the catalysis, exhibiting constant performances in the continuous tests. In addition, the silica also electronically modulated the Cu nanoparticles that result in abundant Cu δ+ species in the catalyst, which minimized the methanol decomposition to improve the methanol selectivity, compared with the silica-free Cu/ZnO/Al 2 O 3 catalyst. As a result, the CZAS exhibited CO 2 conversion at 12.6 % and methanol selectivity at 85.1 %, giving a one-pass methanol yield at 10.7 %. The strategy in this work might provide an efficient route for enhancing the current industrial catalysts.
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
ACS Catalysis
·
2026
·
IF 13.6
Xianglong Meng,Yanjiao Wang,Ruiping Deng,Soryong Chae,Chunzheng Wang,Girolamo Giordano,Zifeng Yan,Hailing Guo,Svetlana Mintova
A strategy for synthesizing bimetallic catalysts confined within zeolite frameworks, offering a promising approach for stabilizing metal species under harsh reaction conditions, is disclosed. A dual-stage synthesis strategy including alkali etching to open the channels of Silicalite-1 (S-1) zeolite, exposing internal hydroxyl defects that serve as anchoring sites for Cu and Zn species, is presented. This was followed by a dry-gel conversion encapsulation step to yield Cu-ZnO@S-1 catalyst. The competitive occupation of these sites by Cu and Zn facilitates the formation of high-density Cu-ZnO interfaces. Under reaction conditions of 3 MPa and 250 °C, the catalyst achieves a methanol selectivity above 99.2% and a space-time yield (STY) of 2.1 g gCu–1 h–1, nearly four times higher than that of copper-containing catalyst (Cu@S-1, 0.54 g gCu–1 h–1) and significantly outperforming the sample prepared by conventional impregnation (Cu-ZnO/S-1, 1.6 g gCu–1 h–1). The oxygen-deficient Cu-ZnO1–x sites at the Cu-ZnO interface are further demonstrated to serve as genuine active centers for methanol synthesis. The methanol formation reaction proceeds via the formate pathway, and the high density of Cu-ZnO1–x sites effectively lowers the activation barrier for the hydrogenation of *HCOO to *H2COO.
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高影响因子
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