Luminescent Functional Metal–Organic Frameworks

Metal nanoparticles stabilized on a support material catalyse many major industrial reactions. Metal-support interactions in these nanomaterials can have a substantial influence on the catalysis, making metal-support interaction modulation one of the few tools able to enhance catalytic performance. This topic has received much attention in recent years, however, a systematic rationalization of the field is lacking due to the great diversity in catalysts, reactions and modification strategies. In this review, we cover and categorize the recent progress in metal-support interaction tuning strategies to enhance catalytic performance for various reactions. Furthermore, we quantify the productivity enhancements resulting from metal-support interaction control that have been achieved in C1 chemistry in recent years. Our analysis shows that up to fifteen-fold productivity enhancement has been achieved, and that metal-support interaction is most impactful for metal nanoparticles smaller than four nanometres. These findings demonstrate the importance of metal-support interaction to improve performance in catalysis. Methods to control the performance of heterogeneous catalysts are extremely relevant to the success of industrial processes. This review provides a rationalization of the effects that metal support interactions have on the reactivity of different catalytic systems, emphasizing strategies to tune such effects.

Control of metal-support interactions in heterogeneous catalysts to enhance activity and selectivity

The efforts to produce photocatalysts operating efficiently under visible light have led to a number of plasmonic photocatalysts, in which noble metal nanoparticles are deposited on the surface of polar semiconductor or insulator particles. In the metal–semiconductor composite photocatalysts, the noble metal nanoparticles act as a major component for harvesting visible light due to their surface plasmon resonance while the metal–semiconductor interface efficiently separates the photogenerated electrons and holes. In this article, we survey various plasmonic photocatalysts that have been prepared and characterized in recent years.

Plasmonic photocatalysts: harvesting visible light with noble metal nanoparticles

Graphene supported heterogeneous catalysts: An overview

Recent advances on preparation and environmental applications of MOF-derived carbons in catalysis

Enhanced catalytic activity over MIL-100(Fe) with coordinatively unsaturated Fe2+/Fe3+ sites for selective oxidation of H2S to sulfur

Developing NH₃ separation technology with high efficiency is very meaningful for the advancement of the NH₃ synthesis process. In this work, a new class of deep eutectic solvents (DESs) were designed by pairing N,N,N′,N′-tetramethyl-1,3-propanediamine dihydrochloride ([TMPDA]Cl₂) with phenol (PhOH) at the molar ratios of 1:3∼7. [TMPDA]Cl₂ + PhOH DESs have multiple weak-acidic groups and viscosities of as low as 48.1 cP at 298.2 K. They also exhibit excellent performance for the separation of NH₃, showing not only efficient and selective but also reversible absorption of NH₃. Especially, the solubilities of NH₃ in [TMPDA]Cl₂ + PhOH DESs at low pressures can reach 4.49 mol/kg of NH₃ at 298.2 K and 13.3 kPa, being superior to those of most of the DESs and ILs reported in the literature. The mechanism of NH₃ absorption was further elucidated by quantum chemistry calculations and ¹H NMR spectra. It is validated that the efficient absorption of NH₃ in DESs origins from the strong interaction of multiple weak-acidic groups of DESs with NH₃.

Designing Low-Viscosity Deep Eutectic Solvents with Multiple Weak-Acidic Groups for Ammonia Separation

Fe-doped γ-Al2O3 porous hollow microspheres for enhanced oxidative desulfurization: Facile fabrication and reaction mechanism

Hierarchically porous γ-Al2O3 nanosheets: Facile template-free preparation and reaction mechanism for H2S selective oxidation

A series of graphitic carbon nitride (CN) in the form of nanosheets with porous structure have been prepared through thermal treatment of bulk CN in air. Compared with the bulk counterpart, the as-generated holey CN nanosheets are larger in specific surface area. Endowed with more active sites and enhanced mass transport ability, the latter display catalytic performance substantially superior to the former, exhibiting higher H2S conversion and S selectivity in the oxidation of H2S to S. Moreover, the CN nanosheets show much better durability than traditional catalysts. It is envisaged that the strategy is a general technique that can be extended to produce porous CN nanosheets from other nitrogen-rich precursors, as well as to prepare other 2D carbon-based materials for potential applications.

Yanning Cao

Papers

Enhanced catalytic activity over MIL-100(Fe) with coordinatively unsaturated Fe2+/Fe3+ sites for selective oxidation of H2S to sulfur

Designing Low-Viscosity Deep Eutectic Solvents with Multiple Weak-Acidic Groups for Ammonia Separation

Fe-doped γ-Al2O3 porous hollow microspheres for enhanced oxidative desulfurization: Facile fabrication and reaction mechanism

Hierarchically porous γ-Al2O3 nanosheets: Facile template-free preparation and reaction mechanism for H2S selective oxidation

Exfoliation of Graphitic Carbon Nitride for Enhanced Oxidative Desulfurization: A Facile and General Strategy