Scalable Synthesis of Holey Deficient 2D Co/NiO Single-Crystal Nanomeshes via Topological Transformation for Efficient Photocatalytic CO2 Reduction.

Preparation of holey, single-crystal, 2D nanomaterials containing in-plane nanosized pores is very appealing for the environment and energy-related applications. Herein, an in situ topological transformation is showcased of 2D layered double hydroxides (LDHs) allows scalable synthesis of holey, single-crystal 2D transition metal oxides (TMOs) nanomesh of ultrathin thickness. As-synthesized 2D Co/NiO-2 nanomesh delivers superior photocatalytic CO2 -syngas conversion efficiency (i.e., VCO of 32460 µmol h-1 g-1 CO and V H 2 ${V_{{{\rm{H}}_2}}}$ of 17840 µmol h-1 g-1 H2 ), with VCO about 7.08 and 2.53 times that of NiO and 2D Co/NiO-1 nanomesh containing larger pore size, respectively. As revealed in high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), the high performance of Co/NiO-2 nanomesh primarily originates from the edge sites of nanopores, which carry more defect structures (e.g., atomic steps or vacancies) than basal plane for CO2 adsorption, and from its single-crystal structure adept at charge transport. Theoretical calculation shows the topological transformation from 2D hydroxide to holey 2D oxide can be achieved, probably since the trace Co dopant induces a lattice distortion and thus a sharp decrease of the dehydration energy of hydroxide precursor. The findings can advance the design of intriguing holey 2D materials with well-defined geometric and electronic properties.

Trade-Off of Metal Sites in Fe-Ni Bimetal Metal-Organic Frameworks for Efficient CO2 Photoreduction with Nearly 100% CO Selectivity.

This work disclosed the trade-off effect of two metal sites, which display distinct, key functionalities in naturally occurring and artificial catalysts for developing an advanced CO2 reduction system. To exploit the metal-organic frameworks (MOFs) as advanced catalysts, we prepared a series of Prussian blue analogues (FeNix PBAs) of tunable Ni/Fe molar ratio without changing the oxidation state of Fe and Ni for use as a photocatalyst in the CO2 reduction reaction (CRR). The FeNi0.66 PBA gives a superior CO yield rate (14.28 mmol·g-1·h-1) with nearly 100% CO selectivity, but the PBA would be basically CRR-inactive without either Ni or Fe. Experimental and calculation studies demonstrate that Fe and Ni display distinct functionalities. Specifically, Fe is an efficient mediator that boosts the electron transfer both from the photosensitizer to FeNix PBA and from FeNix PBA to CO2, and Ni serves as the active site for CO2 adsorption and reduction. Intriguingly, when there is already sufficient Ni in the catalyst, further increase of the Ni content gives marginal gains in the CO2 adsorption affinity that cannot offset the weakened electron transfer due to the Ni excess. The findings can help advance the design of bimetallic MOF catalysts that mimic naturally occurring bimetallic catalysts.

Thin In-Plane In2 O3 /ZnIn2 S4 Heterostructure Formed by Topological-Atom-Extraction: Optimal Distance and Charge Transfer for Effective CO2 Photoreduction.

Exploitation of atomic-level principles to optimize the charge transfer on ultrathin 2D heterostructures is an emerging frontier in relieving the energy and environmental crisis. Herein, a facile "topological-atom-extraction" protocol is disclosed, i.e., selective extraction of Zn from ultrathin half-unit-cell ZnIn2 S4 (HZIS) can embed thin In2 O3 domain into 1.60 nm thick HZIS layer to create an atomically thin in-plane In2 O3 /HZIS heterostructure. Thanks to the optimal distance and capability of charge separation, the in-plane In2 O3 /HZIS heterostructure is among the best ZnIn2 S4 -based CO2 reduction reaction (CRR) photocatalysts, and indeed demonstrates a significant increase (from 6.8- to 128-fold) in CO production rate compared with those of out-plane ZIS@In2 O3 and out-plane In2 O3 -HZIScalcined heterostructures. Density Functional Theory simulation reveals that whereas the out-plane heterostructure has a much smaller ∆q of 0.2-0.25 e, the in-plane heterostructure with "zero distance contact" has an optimal ∆q of 1.05 e between In2 O3 and HZIS that induces remarkable charge redistribution on the in-plane heterojunction interface and creates local electric field confined within the ultrathin layer. The charge redistribution efficiently directs the charge-carrier separation in S-scheme photocatalytic system and endows long-lifetime carrier to CRR active HZIS. The findings demonstrate the strong versatility of engineering atomic-level heterojunctions for efficient catalysts design.

Atomically dispersed and oxygen deficient CuO clusters as an extremely efficient heterogeneous catalyst.

Preparation of high-density and atomically-dispersed clusters is of great importance yet remains a formidable challenge, which precludes rational design of high-performance, ultrasmall heterogeneous catalysts for alleviating the energy and environmental crises. In this study, we demonstrated an appealing non-equilibrium growth model to give sub-2 nm CuO clusters not from the growth of nuclei but from the top-down growth of metastable bulk crystals. These CuO clusters have high density and intriguingly uniform orientation, and are atomically scattered on an inactive ultrathin AlOOH substrate, which has been driven by the lattice matching between the CuO clusters and the utlrathin AlOOH substrate. The catalytic activity of CuO clusters, with the hydrogenation of 4-nitrophenol as a model reaction, proved to be extremely efficient and showed a rate constant of 130.0 s-1 g-1, outperforming the commercial Pd/C catalysts and reported state-of-the-art noble-metal catalysts (1.89-117.2 s-1 g-1). These clusters have abundant interfacial oxygen vacancies (OVs) whose concentration can be regulated, and the OVs are found to be essential, according to density functional theory (DFT) calculations, in reducing the energy barrier of catalytic reduction and significantly boosting the catalytic reaction. These findings could add to the library of crystals downsized to the atomic level and demonstrate how engineering point defects on the sub-nanometer materials help design high-efficient catalysts.