Isolated Ni Atoms Enable Near-Unity CH4 Selectivity for Photothermal CO2 Hydrogenation.

Photothermal hydrogenation of carbon dioxide (CO2) into value-added products is an ideal solution for addressing the energy crisis and mitigating CO2 emissions. However, achieving high product selectivity remains challenging due to the simultaneous occurrence of numerous competing intermediate reactions during CO2 hydrogenation. We present a novel approach featuring isolated single-atom nickel (Ni) anchored onto indium oxide (In2O3) nanocrystals, serving as an effective photothermal catalyst for CO2 hydrogenation into methane (CH4) with a remarkable near-unity (∼99%) selectivity. Experiments and theoretical simulations have confirmed that isolated Ni sites on the In2O3 surface can effectively stabilize the intermediate products of the CO2 hydrogenation reaction and reduce the transition state energy barrier, thereby changing the reaction path to achieve ultrahigh selective methanation. This study provides comprehensive insights into the design of single-atom catalysts for the highly selective photothermal catalytic hydrogenation of CO2 to methane.

Enhancing the photocatalytic efficiency of two-dimensional aluminum nitride materials through strategic rare earth doping.

Two-dimensional (2D) materials demonstrate promising potential as high-efficiency photocatalysts. However, the intrinsic limitations of aluminum nitride (AlN), such as inadequate oxidation capacity, a high carrier recombination rate, and limited absorption of visible light, pose considerable challenges. In this paper, we introduce a novel co-doping technique with dysprosium (Dy) and carbon (C) on a 2D AlN monolayer, aiming to enhance its photocatalytic properties. Our first-principles calculations reveal a reduction in the bandgap and a significant enhancement in the visible light absorption rate of the co-doped Al24N22DyC2 structure. Notably, the distribution of the highest occupied molecular orbital and the lowest unoccupied molecular in proximity to Dy atoms demonstrates favorable conditions for carrier separation. Theoretical assessments of the hydrogen evolution reaction and oxygen evolution reaction activities further corroborate the potential of Al24N22DyC2 as a competent catalyst for photocatalytic reactions. These findings provide valuable theoretical insights for the experimental design and fabrication of novel, high-efficiency AlN semiconductor photocatalysts.

Designed metal-organic π-clusters combining the aromaticity of the metal cluster and ligands for a third-order nonlinear optical response.

The pivotal role of clusters and aromaticity in chemistry is undeniable, but there remains a gap in systematically understanding the aromaticity of metal-organic clusters. Herein, this article presents a novel metal-organic π-cluster, melding both metal-organic chemistry and aromaticity, to guide the construction of structurally stable Os-organic π-clusters. An in-depth analysis of these clusters reveals their bonding attributes, π-electronic composition, and origins of aromaticity, thereby confirming their unique metal-organic π-cluster properties. Furthermore, the Os5 cluster exhibits a promising third-order nonlinear optical (NLO) response, attributable to its narrow band gap and uniform electron/hole distribution, suggesting its potential as an optical switching material. This research introduces a fresh perspective on clusters, centered on delocalization, and broadens the domain of aromaticity studies. It also presents a novel method for designing efficient third-order NLO materials through consideration of the structure-activity relationship.