Title: Optimization and understanding of ZnO nanoarray supported Cu-ZnO-Al₂O₃ catalyst for enhanced CO₂ -methanol conversion at low temperature and pressure

Abstract

Cu-ZnO-Al₂O₃ is the most widely applied catalyst for CO₂ hydrogenation to methanol. However, it is still a challenge to produce methanol using this catalyst under low-temperature (<250 °C) and low-pressure (<10 bar) conditions with desirable yield and selectivity. In this work, by tuning the experimental processing parameters such as solvent, loading amount, and annealing temperature, highly improved ZnO nanoarray supported Cu-ZnO-Al₂O₃ catalysts have been successfully demonstrated. Here, by using organic solvent (N,N-dimethylformamide (DMF), acetone, or isopropanol) for dip-coating loading process instead of deionized (DI) water, Cu-ZnO-Al₂O₃ nanocatalysts was comparatively better dispersed on the nanorod array support with populated and abundant active sites, thus enhancing the methanol yield. With the control of the loading amount and annealing temperature, finely distributed Cu nanoparticles were obtained on the ZnO nanorod surfaces to enhance the interactions between Cu and ZnO nanorod surfaces. Further improvement of the catalyst performance is demonstrated by tuning the reaction space velocity. At 200 °C and 10 bar conditions, the optimized catalyst achieved a methanol yield of 6.46 mol h^–1 kg^–1 with 100 % selectivity. The good stability after prolonged testing of the catalysts demonstrates the potential practical implementation. The in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) measurementsmore » under the 1 bar reveal that the CO₂ hydrogenation to methanol on the ZnO nanoarray supported Cu-ZnO-Al₂O₃ catalyst follows the CO reaction pathway, due to the surface oxygen vacancies on ZnO nanorods which facilitate CO₂ dissociation.« less

Authors:

Sun, Jiyu  ^[1];

• Search DOE PAGES for author "Sun, Jiyu"
• Search DOE PAGES for ORCID "0000-0001-5223-7075"

Liu, Fangyuan  ^[1];

• Search DOE PAGES for author "Liu, Fangyuan"
• Search DOE PAGES for ORCID "0000-0002-3755-7705"

Salahuddin, Usman ^[1]; Wu, Mudi ^[1]; Zhu, Chunxiang ^[1]; Lu, Xingxu  ^[1];

• Search DOE PAGES for author "Lu, Xingxu"
• Search DOE PAGES for ORCID "0000-0003-4518-6585"

Zhang, Bo ^[1]; Zhao, Binchao  ^[1];

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• Search DOE PAGES for ORCID "0000-0003-0772-8873"

Xie, Zhiqiang ^[2]; Ding, Yunjiang ^[1]; Li, Dongsheng ^[3]; Nam, Chang-Yong  ^[4];

• Search DOE PAGES for author "Nam, Chang-Yong"
• Search DOE PAGES for ORCID "0000-0002-9093-4063"

Zhang, Feng-Yuan ^[2]; Gao, Pu-Xian  ^[1]

• Search DOE PAGES for author "Gao, Pu-Xian"
• Search DOE PAGES for ORCID "0000-0002-2132-4392"

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+ Show Author Affiliations

1. Univ. of Connecticut, Storrs, CT (United States)
2. Univ. of Tennessee, Knoxville, TN (United States)
3. Advanced Manufacturing LLC, East Hartford, CT (United States)
4. Brookhaven National Lab. (BNL), Upton, NY (United States)

Publication Date:

Thu Feb 02 00:00:00 EST 2023

Research Org.:

Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:

1969362

Alternate Identifier(s):

OSTI ID: 1923134

Report Number(s):

BNL-224214-2023-JAAM
Journal ID: ISSN 1385-8947

Grant/Contract Number:  

SC0012704; EE0008423

Resource Type:

Accepted Manuscript

Journal Name:

Chemical Engineering Journal

Additional Journal Information:

Journal Volume: 455; Journal ID: ISSN 1385-8947

Publisher:

Elsevier

Country of Publication:

United States

Language:

English

Subject:

77 NANOSCIENCE AND NANOTECHNOLOGY; CO2 hydrogenation; Methanol production; ZnO nanorod arrays; Catalyst-support interaction; Cu-ZnO-Al2O3 catalysts