4.8 Article

Single Solid Precursor-Derived Three-Dimensional Nanowire Networks of CuZn-Silicate for CO2 Hydrogenation to Methanol

Journal

ACS CATALYSIS
Volume 12, Issue 10, Pages 5750-5765

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acscatal.2c00726

Keywords

CO2 hydrogenation; CuZn catalyst; strong metal-support interaction (SMSI); MeOH synthesis; organosilica; nanocatalyst

Funding

  1. National Research Foundation (NRF), Prime Minister's Office, Singapore, under its Campus for Research Excellence and Technological Enterprise (CREATE) program
  2. Agency for Science, Technology, and Research (A*STAR) under its low-carbon energy research funding initiative (LCER-FI)
  3. National University of Singapore under its Flagship Green Energy Program (GEP)

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Hydrogenation of CO2 to produce methanol is an important technology for reducing CO2 emissions and addressing the challenge of climate change. In this study, a Cu-ZnO/Si catalyst with superior structural and compositional properties was synthesized through carefully engineered procedures. The catalyst exhibited high selectivity in producing methanol under moderate conditions, showcasing its potential in CO2 hydrogenation.
Hydrogenation of CO2 to MeOH is one of the most promising technologies in mitigating the emissions of CO2 and tackling the challenge of climate change. In this work, we present a synthetic protocol for preparing a Cu-ZnO-based heterogeneous catalyst supported by siliceous nanowire networks from a single solid precursor with a tunable composition. The resulting Si-Cu-Zn catalysts were evaluated with the MeOH synthesis from the CO2 hydrogenation reaction operated at moderate conditions (30 barg and 200-280 degrees C). A specific MeOH yield of 402 mg(MeOH)center dot g(cu)(-1).h(-1) and a MeOH selectivity of 51% were obtained at 240 degrees C. Such a performance was attributed to several structural and compositional merits, granted through the attentively engineered synthetic procedures. Small Cu nanoparticle (NP) size was achieved and maintained by the high dispersion of Cu to the atomic level in the precatalyst and the incorporation of ZnO as a structural promoter. Moreover, the desirable Cu-ZnO synergistic effect can be further attained from the strong metal-support interaction (SMSI) between the Cu NPs and the partially reduced ZnO phase. Lastly, the robust siliceous nanowire networks provided decent spatial confinement to contain the growth of Cu NPs while offering high accessibility with the macroscopic porous morphology. The catalyst exhibited stable performance over a week's long stability test while keeping its structural integrity intact. Overall, this study may offer an alternative design and synthesis strategy for the well-received Cu-ZnO system to approach its high performance in CO2 hydrogenation.

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