Journal of Energy Chemistry
·
2021
·
IF 9.676
Ziyi Li,Haigang Hao,Jingjing Lu,Chengming Wu,Rui Gao,Jifan Li,Chun-Ling Liu,Wen-Sheng Dong
Here we exquisitely fabricated Cu/ZrO 2 -dp catalysts with plentiful Cu-ZrO 2 interfaces by depositing amorphous ZrO 2 onto Cu nanoparticles for the hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL). With the created plentiful Cu-ZrO 2 interfaces, the optimal catalyst 3Cu/ZrO 2 -dp exhibited exceptional catalytic performance under mild reaction conditions, and achieved the highest GVL mass productivity of 266.0 mmol GVL·h −1 ·g −1 Cu, which was 12.5 and 2.3 times of Cu/ZrO 2 catalysts with equivalent Cu loadings prepared by traditional impregnation (3Cu/ZrO 2 -im) or co-precipitation (3Cu/ZrO 2 -cp). As far as we know, this GVL mass productivity stood at the highest level compared with those obtained using non-noble metal catalysts under similar reaction conditions. By systematic investigation with multiple characterizations, density functional theory (DFT) calculations, and kinetic studies, it was found that interfacial active centers were created at Cu-ZrO 2 interfaces, which contained oxygen vacancies (O v ), negatively charged Cu δ− and partially reduced Zr 3+ . The O v favored the adsorption and activation of LA via its ketone group, while negatively charged Cu δ− was able to enhance heterolysis of H 2 , which resulted in the formation of H + -Cu δ− and Zr 3+ -H − active species via hydrogen spillover. Also, plentiful acid sites, which derived from coordinatively unsaturated and defective Zr species, generated at Cu-ZrO 2 interfaces. With the cooperation of interfacial active centers (Cu δ− -O v -Zr 3+ ) and acid sites, the fabricated 3Cu/ZrO 2 -dp with plentiful Cu-ZrO 2 interfaces achieved excellent catalytic performance for the hydrogenation of LA to GVL. Hence, the synergistic catalysis of Cu-ZrO 2 interfaces provided an effective strategy for designing catalysts with a satisfactory performance for the hydrogenation of LA, which also can be expanded to other hydrodeoxygenation reactions.
研究领域:
催化
·
化学工程
·
材料科学
·
物理化学
✓ 已验证
DOI
高影响因子
ACS Catalysis
·
2023
·
IF 12.9
Nana Gong,Tao Zhang,Minghui Tan,Liyan Wang,Jiaqian Yang,Li Tan,Guohui Yang,Peng Wu,Yingquan Wu,Yisheng Tan
CO hydrogenation to isobutyl alcohol is a promising route for CO transformation to high value-added products. However, the formation mechanism of isobutyl alcohol is complex, and its synthesis requires complex catalysts and harsh reaction conditions, which hinders the identification of active sites. Herein, we efficiently synthesized isobutyl alcohol under mild conditions over a simple Cu–ZrO2 catalyst by decreasing the Cu loading. The space–time yield (STY) of isobutyl alcohol using an optimal CZ-0.11 catalyst was as high as 61.3 g·Lcat–1·h–1 with a CO conversion of 19.2%, far surpassing the STY of the state-of-the-art isobutyl alcohol synthesis (44.6 g·Lcat–1·h–1) under harsh conditions. Decreasing the Cu loading increased the distribution of smaller Cu particles and clarified the structure–activity relationship of Cu–Zr interactions for isobutyl alcohol synthesis. The enhanced Cu–Zr interaction led to the formation of more electron-deficient Cu species on the CZ-0.11 catalyst, which enriched the linearly adsorbed CO on Cu, as demonstrated by in situ diffuse reflectance infrared Fourier-transform spectroscopy. Experimental and theoretical results revealed that coupling of the bicarbonate species on ZrO2 with the linearly adsorbed CO species on electron-deficient Cu clusters promoted the formation of C2 intermediates and finally produced isobutyl alcohol through rapid β-addition. These insights into the active sites for CO hydrogenation to isobutyl alcohol may guide further catalyst designs.
研究领域:
催化化学
·
能源化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
RSC Advances
·
2015
·Vol. 5
·期 56
·45320-45330
·
IF 3.84
Guannan Wang,Limin Chen,Yuhai Sun,Junliang Wu,Mingli Fu,Daiqi Ye
Methanol synthesis from CO2 hydrogenation in a fixed-bed plug flow reactor was investigated over Cu–ZrO2 catalysts supported on CNTs bearing various functional groups. The highest methanol activity (turnover frequency 1.61 × 10−2 s−1, space time yield 84.0 mg gcat−1 h−1) was obtained over the Cu/ZrO2/CNTs catalyst (CZ/CNT-3) with CNTs functionalized by nitrogen-containing groups and Cu loading only about 10.3 wt% under the reaction conditions of 260 °C, 3.0 MPa, V(H2) : V(CO2) : V(N2) = 69 : 23 : 8 and GHSV of 3600 h−1. The catalysts were fully characterized by N2 physisorption, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), H2-temperature-programmed reduction (H2-TPR) and temperature-programmed desorption of H2 (H2-TPD) techniques. The excellent performance of CZ/CNT-3 is attributed to the presence of nitrogen-containing groups on the CNTs surface, which increase the dispersion of copper oxides, promote their reduction, decreases the crystal size of Cu, and enhances H2 and CO2 adsorption capability, thus leading to good catalytic performance towards methanol synthesis.
研究领域:
化学工程
·
催化材料科学
✓ 已验证
产品关联
DOI
高影响因子
RSC Advances
·
2017
·Vol. 7
·期 14
·8709-8717
·
IF 3.108
Yu Hao Wang,Wen Gui Gao,Hua Wang,Yan E. Zheng,Wei Na,Kong Zhai Li
A series of Cu–ZrO2 (CZ) catalysts with different surface area, copper surface area (SCu), oxygen vacancy concentration, and interaction between Cu and ZrO2 features were synthesized. The factors that could affect catalytic activity of CO2 hydrogenation to methanol were investigated. The interaction between Cu and ZrO2 is crucial for determining the catalytic activity. The catalyst possessing the strongest interaction between Cu and ZrO2, exhibited the optimum catalytic activity. The evolution of carbonaceous species and pyridine adsorption over CZ catalysts were investigated using in situ DRIFT spectroscopy. It is found that the hydrogenation of formate species is a rate-limiting step and H spillover plays an important role. The hydrogenation of formate species and H spillover are strongly dependent on the interaction. These results provide a new way of understanding the activity dependence and reaction mechanism of CO2 hydrogenation to methanol over CZ catalysts.
研究领域:
催化化学
·
能源化学
✓ 已验证
产品关联
DOI
高影响因子
Green Energy & Environment
·
2020
·
IF 6.395
Yuewen Shao,Tingting Wang,Kai Sun,Zhanming Zhang,Lijun Zhang,Qingyin Li,Shu Zhang,Guangzhi Hu,Xun Hu
Oxides with different crystal phases can have important effects on the configuration of surface atoms, which can further affect the distribution of hydrogenation sites and acidic sites as well as the competitions of these varied types of catalytic sites. This could be potentially used to tailor the distribution of the products. In this study, zirconium oxides with different crystal phases supported copper catalysts were prepared for the hydrogenation of the biomass-derived furfural, vanillin, etc. The results showed that both calcination temperature and Cu species affected the shift of zirconia from tetragonal phase to the monoclinic phase. Monoclinic zirconia supported copper catalyst can effectively catalyze the hydrogenation of furfural to furfuryl alcohol via hydrogenation route due to its low amount of Brønsted acidic sites, although the surface area and the exposed metallic Cu surface area were much lower than the tetragonal zirconia supported copper catalyst. Zirconia with tetragonal or tetragonal/monoclinic phases supported copper catalysts contain abundant acidic sites and especially the Brønsted acidic sites, which catalyzed mainly the conversion of furfural via the acid-catalyzed routes such as the acetalization, rather than the hydrogenation. The acidic sites over the Cu/ZrO 2 catalyst played more predominant roles than the hydrogenation sites in determining the conversion of the organics like furfural and vanillin.
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Coatings Technology and Research
·
2022
·Vol. 20
·期 3
·869-881
·
IF 2.339
Li Xianwen,Xu Xinmeng,Zhang Faai
Hydroxyl acrylate emulsion was prepared firstly by the semicontinuous seeded emulsion polymerization, and then adding polyaniline (PANI)/Cu/ZrO 2 ternary nanocomposites, two-component waterborne polyurethane (2 K WPU) composite coatings with antistatic and antibacterial properties were obtained by mixing the emulsion with hydrophilic modified polyisocyanate. The structure and morphology of the PANI/Cu/ZrO 2 were observed by Fourier transform infrared spectroscopy, scanning electron microscopy, and X-ray diffractometer. The thermal, antistatic, antibacterial, anticorrosion, and mechanical properties of the 2 K WPU composite coatings were determined. The results showed that the addition of the ternary nanocomposites increased the antistatic, antibacterial, anticorrosion, and mechanical properties of the 2 K WPU coating. The initial decomposition temperature increased from 200 to 225°C, and the tensile strength increased by 44.4%. The coatings still maintained good impact strength of 50/50 kg cm, adhesion of grade 2, flexibility of 1 mm, pendulum hardness of 293 s, and the gloss (60°) of 119.4.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF MATERIALS SCIENCE
·
2024
·Vol. 59
·期 9
·3970-3983
·
IF 3.5
Liu Sisi,Deng Yuxing,Jiang Shengqiang,Liu Jingang
Poly (2-methacryloyloxyethyl phosphorylcholine) (PMPC), as a highly hydrophilic as well as biocompatible material, has been widely used in biomedical applications. In this study, the friction reduction and wear resistance of HXLPE were improved by grafting PMPC on its surface. However, the PMPC will be sheared off during friction, which is difficult to meet the long-term service requirements of artificial joints. This can be achieved by improving the lubrication environment to minimize PMPC shedding. To simulate the human lubrication environment, free PMPC (lubrication factor) and Cu 2+ (transition group metal ion catalyst) were added to neonatal bovine serum (NBCS). When the friction pair consisting of grafted PMPC-modified HXLPE and Cu/ZrO 2 ceramics is rubbed therein, the grafted PMPC interacts with the free PMPC, while Cu 2+ catalyzes the oxidative hydrolysis of serum proteins into carbon-containing small molecules and adsorbs on the surface of the Cu/ZrO 2 ceramics to form a carbon-rich lubrication layer. The composite lubrication layer consisting of grafted-free PMPC and carbon-rich lubrication layer provides good load-bearing and lubrication properties at the friction interface. And the wear rate is reduced by 45% compared to rubbing in deionized water. This technique can reduce the shedding of grafted PMPC state and improve the load-bearing performance of the interfacial lubrication layer, thus reducing the wear of HXLPE and prolonging the service life of the artificial joint.
研究领域:
生物医学工程
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材料科学
·
摩擦学
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表面工程
·
高分子科学
✓ 已验证
DOI
高影响因子
Molecular Catalysis
·
2019
·
IF 2.938
Xin Li,Haixing Wang,Peiyong Sun,Shenghong Zhang,Zhilong Yao
Cu/ZrO 2 catalysts with or without boron modification were prepared, characterized, and evaluated in the hydrogenation of sec -butyl acetate (SBA) to 2-butanol. Cu/ZrO 2 catalysts were active for the hydrogenation of SBA but suffered serious deactivation due to the leaching of Cu. Introduction of boron onto Cu/ZrO 2 catalysts improved the dispersion of Cu species, the surface Cu + /Cu 0 ratios, and the catalyst stability owing to the enhanced interaction between Cu species and support. However, it decreased the intrinsic activity of Cu towards the hydrogenation of SBA and complicated the reaction network by accelerating acid-catalyzed isomerization and transesterification processes as a result of the strengthened acidity by boron. A further kinetic analysis unravelled that the reaction orders for SBA and H 2 are 0.58 and 0.83, respectively, and the apparent activation energy is 47 kJ/mol. Such understanding of the structural evolution of CuB/ZrO 2 catalysts and the consequent catalytic performances with the B contents may provide insights useful for the design of Cu catalysts with desirable stability for hydrogenation of SBA and other esters.
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2025
·
IF 4.3
Wenbin Huang,Kaining Wang,Han Yang,Tianyu Bai,Yasong Zhou,Qiang Wei,Minghan Han
CO 2 hydrogenation to methanol emerges as a promising strategy, offering a dual advantage of carbon dioxide fixation and the production of a valuable liquid fuel and chemical feedstocks. However, its industrial application is limited by the high stability of the CO 2 molecule, resulting in low CO 2 conversion and methanol selectivity. In this work, a series of Ce-doped Cu-ZrO 2 catalysts were synthesized by an oxalic acid gel co-precipitation method, and the effect of Ce/Zr molar ratios on catalyst structure and catalytic performance were investigated. Comprehensive characterization techniques, including XRD, N 2 physical adsorption–desorption, HRTEM, H 2 -TPR, XPS, CO 2 /H 2 -TPD and DFT calculation were employed to analyze the influence of Ce doping on oxygen vacancy concentration, surface basicity distribution, electron transfer, and catalytic performance. The results demonstrate that the CC 0.4 Z catalyst (n(Ce)/n(Zr) = 0.4) forms a Ce 0.4 ZrO solid solution structure, significantly enhancing CuO dispersion and generating abundant Cu δ+ -Ce 0.4 ZrO interfacial sites and oxygen vacancies. These features synergistically promote CO 2 /H 2 adsorption and activation while stabilizing Cu + species. Under optimized reaction conditions (260 ℃, 3.0 MPa, 9000 h −1 ), the CC 0.4 Z catalyst exhibits outstanding performance: CO 2 conversion of 14.6 %, methanol selectivity of 74.1 %, and a methanol yield of 10.8 %. Compared to the unmodified catalyst, this represents an increase of 5.8 percentage points in CO 2 conversion and 6.3 percentage points in methanol yield, providing a novel catalyst design strategy for efficient CO 2 conversion.
研究领域:
催化化学
·
环境化学
·
材料科学
·
化学工程
·
可再生能源
✓ 已验证
产品关联
DOI
高影响因子
CATALYSIS TODAY
·
2017
·
IF 4.636
Yuhai Sun,Limin Chen,Yunfeng Bao,Guannan Wang,Yujun Zhang,Mingli Fu,Junliang Wu,Daiqi Ye
Cu-ZrO 2 catalysts supported on nitrogen-doped CNTs were tested for CO 2 hydrogenation to methanol in a fixed-bed plug flow reactor. The characterization results indicate that the presence of pyridinic nitrogen increases the copper oxide dispersion, promotes their reduction, decreases the Cu particle size and enhances H 2 adsorption capability; the activated CO 2 adsorption predominantly controls CO 2 conversion. In addition, pyridinic nitrogen contributes to the strong adsorption of CO 2 , stimulating methanol formation, while pyrrolic nitrogen contributes to the medium adsorption of CO 2 , mainly boosting CO formation. Thus, pyridinic nitrogen dominant CNTs supported catalyst (CZ/CNT-N) possesses more active sites compared with the other three catalysts, leading to maximum methanol yield (8.64%) and space time yield (102.21 mg g −1 cat h −1 ); pyrrolic nitrogen dominant CNTs supported catalyst (CZ/CNT-NH 2 ) obtains more highly active structure, giving the highest intrinsic activity (TOF values).
研究领域:
化学工程
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
·
2020
·
IF 12.35
Zihao Zhang,Meizan Jing,Hao Chen,Francis Okejiri,Jixing Liu,Yan Leng,Haolan Liu,Weiyu Song,Zhaoyin Hou,Xiuyang Lu,Jie Fu,Jian Liu
The catalytic transformation of renewable fatty acids into value-added fatty alcohols without the use of gaseous hydrogen is a versatile technique for the utilization of microalgae and waste cooking oil, where Cu-based catalysts are considered to be the most suitable candidate. However, the interpretation of the structure–reactivity relationship caused by different crystal types of carriers and the metal–support interface is not well understood. Herein we synthesized ZrO2-supported Cu nanoparticle catalysts via different preparation methods and reduction temperatures under similarly exposed surface facets and Cu valency but different polymorphic phases of ZrO2 (monoclinic ZrO2: m-ZrO2; tetragonal ZrO2: t-ZrO2) and the metal–support interface. Interestingly, the as-synthesized Cu/t-ZrO2 catalysts showed remarkably better catalytic performance than Cu/m-ZrO2 for the in situ hydrogenation of lauric acid in the methanol–water system. Combined experimental and density functional theory (DFT) calculation results ascribed the lower efficiency of m-ZrO2 as a carrier to weakly adsorbed reactant and intermediate molecules as well as the absence of an oxygen vacancy in the crystal phase. The interface-rich Cu/t-ZrO2 catalysts displayed higher activity normalized to the surface-exposed Cu sites toward lauryl alcohol production than the interface-deficient counterparts. DFT calculation results further revealed that this metal–support interface plays an important role in promoting the C–O bond or H–H bond cleavage in two possible reaction routes, thus reducing the activation barrier of the overall reaction.
研究领域:
催化化学
·
可再生能源
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
RSC Advances
·
2019
·Vol. 9
·期 52
·30439-30447
·
IF 3.049
Yongsheng Wang,Zhenzhen Zhao,Yunlu Zhao,Xiaolin Lan,Weixiang Xu,Li Chen,Dongjie Guo,Zhengkang Duan
The sintering resistance of supported Cu nanoparticle (NP) catalysts is crucial to their practical application in the dehydrogenation of diethanolamine (DEA). In this paper, co-precipitation, hydrothermal synthesis, and sol–gel condensation are used to form a new support material through chemical bonding between graphene oxide and ZrO2. The composite carriers prepared by the three methods are mixed with copper nitrate and ground using a ball mill. A series of Cu/ZrO2-reduced graphene oxide (RGO) composites were prepared by calcination under nitrogen at 450 °C for 3 h and hydrogen reduction at 250 °C for 4 h. The conversion of DEA to iminodiacetic acid (IDA) reached 96% with the Cu/ZrO2-RGO catalyst prepared by hydrothermal synthesis. The conversion rate of DEA is more than 80% following the reuse of the CZG-2 catalyst for twelve cycles. The various physicochemical characterization techniques show that the Cu/ZrO2-RGO layered and wrinkled nanostructures can improve catalytic stability and suppress the sintering of the supported Cu NPs during the catalytic dehydrogenation of diethanolamine. A synergistic effect between the RGO and the Cu nanoparticles is observed. The Cu nanoparticles with RGO have a better dispersibility, and a new nano-environment is created, which is the key to improving the efficiency of diethanolamine dehydrogenation. These new Cu/ZrO2-RGO catalysts show increased durability compared to commercially produced Cu/ZrO2 catalysts and show promise for practical applications involving diethanolamine dehydrogenation.
研究领域:
材料科学
·
化学工程
·
催化
·
纳米技术
✓ 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）