Highly Dispersed Pd@ZIF-8 for Photo-Assisted Cross-Couplings and CO2 to Methanol: Activity and Selectivity Insights.

Our study unveils a pioneering methodology that effectively distributes Pd species within a zeolitic imidazolate framework-8 (ZIF-8). We demonstrate that Pd can be encapsulated within ZIF-8 as atomically dispersed Pd species that function as an excited-state transition metal catalyst for promoting carbon-carbon (C-C) cross-couplings at room temperature using visible light as the driving force. Furthermore, the same material can be reduced at 250 °C, forming Pd metal nanoparticles encapsulated in ZIF-8. This catalyst shows high rates and selectivity for carbon dioxide hydrogenation to methanol under industrially relevant conditions (250 °C, 50 bar): 7.46 molmethanol molmetal-1 h-1 and >99%. Our results demonstrate the correlations of the catalyst structure with the performances at experimental and theoretical levels.

Thermochemical CO2 Reduction Catalyzed by Homometallic and Heterometallic Nanoparticles Generated from the Thermolysis of Supramolecularly Assembled Porous Metal-Adenine Precursors.

A family of unprecedented supramolecularly assembled porous metal-organic compounds (SMOFs), based on [Cu6M(µ-adeninato)6(µ3-OH)6(µ-H2O)6]2+ cations (MII: Cu, Co, Ni, and Zn) and different dicarboxylate anions (fumarate, benzoate, and naphthalene-2,6-dicarboxylate), have been employed as precursors of catalysts for the thermocatalytic reduction of CO2. The selected metal-organic cation allows us to tune the composition of the SMOFs and, therefore, the features and performance of the final homometallic and bimetallic catalysts. These catalysts were obtained by thermolysis at 600 °C under a N2 atmosphere and consist of big metal particles (10-20 µm) placed on the surface of the carbonaceous matrix and very tiny metal aggregates (<10 nm) within this carbonaceous matrix. The latter are the most active catalytic sites for the CO2 thermocatalytic reduction. The amount of this carbonaceous matrix correlates with the organic content present in the metal-organic precursor. In this sense, CO2 thermocatalytic reduction experiments performed over the homometallic, copper only, catalysts with different carbon contents indicate that above a certain value, the increase of the carbonaceous matrix reduces the overall performance by encapsulating the nanoparticles within this matrix and isolating them from interacting with CO2. In fact, the best performing homometallic catalyst is that obtained from the precursor containing a small fumarate counterion. On the other hand, the structural features of these precursors also provide a facile route to work with a solid solution of nanoparticles as many of these metal-organic compounds can replace up to 1/7 of the copper atoms by zinc, cobalt, or nickel. Among these heterometallic catalysts, the best performing one is that of copper and zinc, which provides the higher conversion and selectivity toward CO. XPS spectroscopy and EDX mappings of the latter catalyst clearly indicate the presence of Cu1-xZnx nanoparticles covered by small ZnO aggregates that provide a better CO2 adsorption and easier CO release sites.

Copper nanoparticles encapsulated in zeolitic imidazolate framework-8 as a stable and selective CO2 hydrogenation catalyst.

Metal-organic frameworks have drawn attention as potential catalysts owing to their unique tunable surface chemistry and accessibility. However, their application in thermal catalysis has been limited because of their instability under harsh temperatures and pressures, such as the hydrogenation of CO2 to methanol. Herein, we use a controlled two-step method to synthesize finely dispersed Cu on a zeolitic imidazolate framework-8 (ZIF-8). This catalyst suffers a series of transformations during the CO2 hydrogenation to methanol, leading to ~14 nm Cu nanoparticles encapsulated on the Zn-based MOF that are highly active (2-fold higher methanol productivity than the commercial Cu-Zn-Al catalyst), very selective (>90%), and remarkably stable for over 150 h. In situ spectroscopy, density functional theory calculations, and kinetic results reveal the preferential adsorption sites, the preferential reaction pathways, and the reverse water gas shift reaction suppression over this catalyst. The developed material is robust, easy to synthesize, and active for CO2 utilization.

Is cavitation a truly sensible choice for intensifying photocatalytic oxidation processes? - Implications on phenol degradation using ZnO photocatalysts.

Phenols are recalcitrant compounds that constitute the majority of organic contaminants in industrial wastewaters. Their removal at large scales require a combination of various processes to reach the desired discharge quality. An extensive body of work has already been published in the area of phenol removal from wastewater, however none of them have focussed on a truly 'sensible' approach for coupling advanced oxidation processes (AOPs). Rather, a higher removal efficiency was targeted by unduly complicating the process by combining multiple AOPs. The most influential AOP as the primary method typically driven by the nature of the pollutant should form the basis for a hybrid AOP followed by a complementary AOP to intensify the oxidation process. This strategy is lacking in current literature. We address this knowledge gap directly by systematically identifying the best hybrid process for ZnO mediated photocatalysis of phenol. Either a cavitation mediated pre-treatment of ZnO or cavitation-photocatalysis-peroxide based hybrid AOP was investigated. While the pre-treatment approach led to >25% increase in phenol oxidation compared to bare ZnO photocatalysis, the hydrodynamic cavitation-photocatalysis-peroxide based system was found to have a cavitational yield 5 times higher than its acoustic cavitation counterpart. A new phenomenon known as the 'pseudo staggered effect' was also observed and established in hydrodynamic cavitation mediated photocatalysis-peroxide hybrid process for the first time. While we demonstrated that cavitation is a truly 'sensible' choice to enhance photocatalysis, the nature of the pollutant under investigation must always be the key driver when designing such hybrid AOPs.