ABSTRACT
In modern heterogeneous catalysis, it remains highly challenging to create stable, low-cost, mesoporous 2D photo-/electro-catalysts that carry atomically dispersed active sites. In this work, a general shape-preserving amorphous-to-crystalline transformation (ACT) strategy is developed to dope various transition metal (TM) heteroatoms in ZrO2, which enabled the scalable synthesis of TMs/oxide with a mesoporous 2D structure and rich defects. During the ACT process, the amorphous MZrO2 nanoparticles (M = Fe, Ni, Cu, Co, Mn) are deposited within a confined space created by the NaCl template, and they transform to crystalline 2D ACT-MZrO2 nanosheets in a shape-preserving manner. The interconnected crystalline ACT-MZrO2 nanoparticles thus inherit the same structure as the original MZrO2 precursor. Owing to its rich active sites on the surface and abundant oxygen vacancies (OVs), ACT-CoZrO2 gives superior performance in catalyzing the CO2-to-syngas conversion as demonstrated by experiments and theoretical calculations. The ACT chemistry opens a general route for the scalable synthesis of advanced catalysts with precise microstructure by reconciliating the control of crystalline morphologies and the dispersion of heteroatoms.
ABSTRACT
The synthesis and characterization of an FeII /FeIII metal-organic framework (MOF) nanocrystal with spatial heterogeneity that arises from the non-uniform distribution of different valence states is disclosed. The FeII /FeIII -Ni Prussian blue analog (PBA) delivers superior photocatalytic performance in the selective CO2 reduction reaction thanks to the strong FeII /FeIII coupling, with CO yield up to 12.27 mmol g-1 h-1 and 90.6% selectivity under visible-light irradiation. Density functional theory calculation and experimental studies prove that the spatial heterogeneity of FeII /FeIII in the individual MOF nanocrystal not only directs and expedites the charge transfer within a catalyst particle but also creates the heterogeneity of catalytically-active Ni sites for efficient CO2 photoreduction. The current findings add to a growing literature of materials with compositional heterogeneity and provide a reference for future research.
ABSTRACT
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.
