Cu@ZIF-8 derived inverse ZnO/Cu catalyst with sub-5 nm ZnO for efficient CO2 hydrogenation to methanol

Hu, Bing; Yin, Yazhi; Zhong, Zixin; Wu, Dengdeng; Guo-liang, Liu; Hong, Xia

doi:10.1039/c8cy02546k

Cited by 41 publications

(29 citation statements)

References 57 publications

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“…The results found that 10 wt% CuZn/rGO catalyst exhibited a good activity for the CO 2 hydrogenation, achieving 26 % CO 2 conversion, methanol selectivity of 51%, and 424 ± 18 mg methanol at 250°C under 15 bar after 5 h on a stream (Deerattrakul et al, 2016). With MOF as a support or component of catalyst, very high methanol selectivity (up to 100%) was reported (Rungtaweevoranit et al, 2016;An et al, 2017;Hu et al, 2019). Still, its application suffers from serious challenges that are undesirable for industrial applications-low conversion and instability at high temperatures.…”

Section: Non-metal Oxide Supportsmentioning

confidence: 95%

Improving the Cu/ZnO-Based Catalysts for Carbon Dioxide Hydrogenation to Methanol, and the Use of Methanol As a Renewable Energy Storage Media

2020

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Heterogeneous catalytic hydrogenation of carbon dioxide (CO2) to methanol is a practical approach to mitigating its greenhouse effect in the environment while generating good economic profits. Though applicable on the industrial scale through the syngas route, the catalyst of Cu/ZnO/Al2O3 suffers from a series of technical problems when converting CO2 to methanol directly, which include low single-pass conversion, low methanol selectivity, requiring high pressure and fast deactivation by the reverse water gas shift reaction. Over the years, intensive research efforts have been devoted to proffering solutions to these problems by modifying the existing catalyst or developing new active catalysts. However, the open question is if this type of widely used industrial catalyst still promising for CO2 methanolizing reaction or not? This paper reviews the history of the methanol production in industry, the impact of CO2 emission on the environment, and analyzes the possibility of the Cu/ZnO-based catalysts for the direct hydrogenation of CO2 to methanol. We not only address the theoretical and technical aspects but also provide insightful views on catalyst development.

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Section: Non-metal Oxide Supportsmentioning

confidence: 95%

Improving the Cu/ZnO-Based Catalysts for Carbon Dioxide Hydrogenation to Methanol, and the Use of Methanol As a Renewable Energy Storage Media

2020

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“…It has been documented that copper-based catalysts are highly active in CO2 hydrogenation to methanol [11][12][13][14] , which have been widely used in this process of CO2 hydrogenation owing to its high catalytic performance and the moderate price. Typically, Cu species always combine with metal oxides (such as ZnO 10,[15][16][17][18][19] , ZrO2 [6][7][8][20][21][22][23][24][25] , and CeO2 [26][27][28][29] ) making more active sites for better performance towards methanol synthesis.…”

Section: Introductionmentioning

confidence: 99%

Cu@UiO-66 Derived Cu+-ZrO2 Interfacial Sites for Efficient CO2 Hydrogenation to Methanol

王艳秋¹,

钟子欣²,

刘唐康³

et al. 2020

Acta Physico Chimica Sinica

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Cu/ZrO2 catalysts have demonstrated effective in hydrogenation of CO2 to methanol, during which the Cu-ZrO2 interface plays a key role. Thus, maximizing the number of Cu-ZrO2 interface active sites is an effective strategy to develop ideal catalysts. This can be achieved by controlling the active metal size and employing porous supports. Metal-organic frameworks (MOFs) are valid candidates because of their rich, openframework structures and tunable compositions. UiO-66 is a rigid metal-organic skeleton material with excellent hydrothermal and chemical stability that comprises Zr as the metal center and terephthalic acid (H2BDC) as the organic ligand. Herein, porous UiO-66 was chosen as the ZrO2 precursor, which can confine Cu nanoparticles within its pores/defects. As a result, we constructed a Cu-ZrO2 nanocomposite catalyst with high activity for CO2 hydrogenation to methanol. Many active interfaces could form when the catalysts were calcined at a moderate temperature, and the active interface was optimized by adjusting the calcination temperature and active metal size. Furthermore, the Cu-ZrO2 interface remained after CO2 hydrogenation to methanol, as confirmed by transmission electron microscopy (TEM), demonstrating the stability of the active interface. The catalyst structure and hydrogenation activity were influenced by the content of the active component and the calcination temperature; therefore, these parameters were explored to obtain an optimized catalyst. At 280 °C and 4.5 MPa, the optimized CZ-0.5-400 catalyst gave the highest methanol turnover frequency (TOF) of 13.4 h −1 with a methanol space-time yield (STY) of 587.8 g•kg −1 •h −1 (calculated per kilogram of catalyst, the same below), a CO2 conversion of 12.6%, and a methanol selectivity of 62.4%. In situ diffusereflectance infrared Fourier transform spectroscopy (DRIFTS) of CO adsorption over the optimized catalyst revealed a predominant, unreducible Cu + species that was also identified by X-ray photoelectron spectroscopy (XPS). The favorable activity observed was due to this abundant Cu + species coming from the Cu + -ZrO2 interface that served as the methanol synthesis active center and acted as a bridge for transporting hydrogen from the active Cu species to ZrO2. In addition, the oxygen vacancies of ZrO2 promoted the adsorption and activation of CO2. These vacancies and Cu + trapped in the ZrO2 lattice are the active sites for methanol synthesis from CO2 hydrogenation. The X-ray diffraction (XRD) patterns of the catalyst before and after reaction revealed the stability of its structure, which was further verified by time-on-stream (TOS) tests. Furthermore, in situ DRIFTS and temperature-programmed surface reaction-mass spectroscopy (TPSR-MS) revealed the reaction mechanism of CO2 hydrogenation to methanol, which followed an HCOO-intermediated pathway.

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“…Generally, Cu–ZnO and Fe 3 O 4 are active for rWGSR 43 and Cu–ZnO interfaces are also responsible for methanol production. 44 As for the production of higher carbon products, iron carbide has been regarded as the active site for C–O dissociation and C–C coupling while the Cu site for C–O non-dissociative activation. 45,46 The active Cu–Fe x C interfaces are able to produce C 2+ alcohols.…”

Section: Resultsmentioning

confidence: 99%

Selective C₂₊ alcohol synthesis by CO₂ hydrogenation via a reaction-coupling strategy

Wang

Zhang

et al. 2022

Catal. Sci. Technol.

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Cu@ZIF-8 derived inverse ZnO/Cu catalyst with sub-5 nm ZnO for efficient CO₂ hydrogenation to methanol

Abstract: Cu@ZIF-8 derived inverse ZnO/Cu with sub-5 nm ZnO acts as an efficient catalyst for CO2 hydrogenation to methanol.

Cited by 41 publications

References 57 publications

Improving the Cu/ZnO-Based Catalysts for Carbon Dioxide Hydrogenation to Methanol, and the Use of Methanol As a Renewable Energy Storage Media

Improving the Cu/ZnO-Based Catalysts for Carbon Dioxide Hydrogenation to Methanol, and the Use of Methanol As a Renewable Energy Storage Media

Cu@UiO-66 Derived Cu<sup>+</sup>-ZrO<sub>2</sub> Interfacial Sites for Efficient CO<sub>2</sub> Hydrogenation to Methanol

Selective C₂₊ alcohol synthesis by CO₂ hydrogenation via a reaction-coupling strategy

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Cu@ZIF-8 derived inverse ZnO/Cu catalyst with sub-5 nm ZnO for efficient CO2 hydrogenation to methanol

Abstract: Cu@ZIF-8 derived inverse ZnO/Cu with sub-5 nm ZnO acts as an efficient catalyst for CO2 hydrogenation to methanol.

Cited by 41 publications

References 57 publications

Improving the Cu/ZnO-Based Catalysts for Carbon Dioxide Hydrogenation to Methanol, and the Use of Methanol As a Renewable Energy Storage Media

Improving the Cu/ZnO-Based Catalysts for Carbon Dioxide Hydrogenation to Methanol, and the Use of Methanol As a Renewable Energy Storage Media

Cu@UiO-66 Derived Cu<sup>+</sup>-ZrO<sub>2</sub> Interfacial Sites for Efficient CO<sub>2</sub> Hydrogenation to Methanol

Selective C2+ alcohol synthesis by CO2 hydrogenation via a reaction-coupling strategy

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Cu@ZIF-8 derived inverse ZnO/Cu catalyst with sub-5 nm ZnO for efficient CO₂ hydrogenation to methanol

Selective C₂₊ alcohol synthesis by CO₂ hydrogenation via a reaction-coupling strategy