二酸化炭素からのメタノール合成のための活性点空間分離戦略を提案 (Spatially Decoupling Active-sites Strategy Proposed for Efficient Methanol Synthesis from Carbon Dioxide)

2026-03-16 中国科学院（CAS）

＜関連情報＞

• https://english.cas.cn/newsroom/research-news/202603/t20260311_1152403.shtml
• https://www.cell.com/chem/abstract/S2451-9294(26)00008-2

CO2のメタノールへの水素化における活性と選択性のトレードオフの解明 Disentangling the activity-selectivity trade-off in CO2 hydrogenation to methanol

Habib Zada ∙ Jiafeng Yu (俞佳枫) ∙ Chuanyan Fang (方传艳) ∙ Jian Sun (孙剑)
Chem  Published:March 13, 2026
DOI:https://doi.org/10.1016/j.chempr.2026.102942

Graphical abstract

The bigger picture

Thermodynamically, low temperatures favor the CO₂ hydrogenation to methanol reaction, whereas elevated temperatures tend to trigger the endothermic reverse water-gas shift side reaction, leading to an activity-selectivity trade-off for traditional Cu-based catalysts. Balancing thermodynamic constraints with kinetic requirements is thus critical for efficient methanol synthesis. This dilemma stems from the inherent catalytic behavior of CO₂ activation, followed by undesired C–O bond cleavage on Cu active sites, which mainly produces CO rather than methanol. Here, we introduce a novel spatial decoupling strategy via a sputtering technique and strong metal-support interaction (SMSI)-driven surface engineering. The SMSI-induced ZnO_x migration alters the surface chemistry of Cu-based catalysts, transferring CO₂ adsorption from Cu to ZrO₂ sites while retaining H₂ activation on Cu. Unlike conventional catalyst design focused on single-component active sites, this approach creates a dual-site catalytic system that integrates the selective methanol synthesis capability of ZrO₂ with the efficient H₂ dissociation of Cu. It efficiently suppresses the formation of the thermodynamically favored CO by-product without sacrificing activity, thus achieving a long-sought methanol yield. The tailoring of active sites for CO₂ and H₂ is conducted to shed light on the structure-activity relationship in the Cu–Zn–Zr ternary system at elevated temperatures. This work not only demonstrates the feasibility of using spatial site decoupling for resolving catalytic trade-offs but also opens a new class of materials and design paradigms for sustainable methanol synthesis and carbon-neutral fuel production.

Highlights

• The activity-selectivity trade-off is broken in the CO₂ hydrogenation to methanol reaction
• An exceptional 92% methanol selectivity is achieved at 300°C on Cu-based catalysts
• Strong metal-support interaction can induce decoupled adsorption on separated sites
• Activation of H₂ and CO₂ on dual sites favors methanol synthesis via the formate pathway

Summary

Cu-based catalysts for CO₂ hydrogenation show outstanding performance but often face an activity-selectivity trade-off. Herein, we introduced Cu nanoparticles onto ZnZr oxides via a sputtering method, inducing ZnO migration over Cu surfaces by a strong metal-support interaction. This enhances the CO₂ conversion by 5-fold compared with ZnZr oxide catalysts and achieves 92% methanol selectivity, significantly outperforming commercial CuZnAl (11%) at 300°C, resulting in a methanol space-time yield of 1.2 g⸱g_cat⁻¹⸱h⁻¹. Characterization reveals that the coverage suppresses CO₂ activation at Cu sites and C‒O bond breaking before hydrogenation to reduce CO production. CO₂ preferentially adsorbs on ZrO₂ sites with both O atoms, following a formate pathway, where activated H from Cu sites attacks C without breaking the O–C–O bonds. Decoupling activation sites drives the hydrogenation pathway toward methanol over CO, even at high temperatures. This spatial arrangement of catalytic sites provides key insights for designing high-performance catalysts by weakening undesired functions.