Oxygen-deficient metal oxides supported nano-intermetallic InNi<sub>3</sub>C<sub>0.5</sub> toward efficient CO<sub>2</sub> hydrogenation to methanol.

Meng, Chao; Zhao, Guofeng; Shi, Xue-Rong; Chen, Pengjing; Liu, Ye; Lu, Yong · Sci Adv · 2021

basic_science · Level V

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Abstract

Direct CO<sub>2</sub> hydrogenation to methanol using renewable energy-generated hydrogen is attracting intensive attention, but qualifying catalysts represents a grand challenge. Pure-/multi-metallic systems used for this task usually have low catalytic activity. Here, we tailored a highly active and selective InNi<sub>3</sub>C<sub>0.5</sub>/ZrO<sub>2</sub> catalyst by tuning the performance-relevant electronic metal-support interaction (EMSI), which is tightly linked with the ZrO<sub>2</sub> type-dependent oxygen deficiency. Highly oxygen-deficient monoclinic-ZrO<sub>2</sub> support imparts high electron density to InNi<sub>3</sub>C<sub>0.5</sub> because of the considerably enhanced EMSI, thereby enabling InNi<sub>3</sub>C<sub>0.5</sub>/monoclinic-ZrO<sub>2</sub> with an intrinsic activity three or two times as high as that of InNi<sub>3</sub>C<sub>0.5</sub>/amorphous-ZrO<sub>2</sub> or InNi<sub>3</sub>C<sub>0.5</sub>/tetragonal-ZrO<sub>2</sub> The EMSI-governed catalysis observed in the InNi<sub>3</sub>C<sub>0.5</sub>/ZrO<sub>2</sub> system is extendable to other oxygen-deficient metal oxides, in particular InNi<sub>3</sub>C<sub>0.5</sub>/Fe<sub>3</sub>O<sub>4</sub>, achieving 25.7% CO<sub>2</sub> conversion with 90.2% methanol selectivity at 325°C, 6.0 MPa, 36,000 ml g<sub>cat</sub> <sup>-1</sup> hour<sup>-1</sup>, and H<sub>2</sub>/CO<sub>2</sub> = 10:1. This affordable catalyst is stable for at least 500 hours and is also highly resistant to sulfur poisoning.