Dual Microenvironment Modulation of Pd Nanoparticles in Covalent Organic Frameworks for Semihydrogenation of Alkynes

The chemical microenvironment modulation of metal nanoparticles (NPs) holds promise for tackling the long-lasting challenge of the trade-off effect between activity and selectivity in catalysis. Herein, ultrafine PdCu₂ NPs incorporated into covalent organic frameworks (COFs) with diverse groups on their pore walls have been fabricated for the semihydrogenation of alkynes. The Cu species, as the primary microenvironment of Pd active sites, greatly improves the selectivity. The functional groups as the secondary microenvironment around PdCu₂ NPs effectively regulate the activity, in which PdCu₂ NPs encapsulated in the COF bearing −CH₃ groups exhibit the highest activity with >99 % conversion and 97 % selectivity. Both experimental and calculation results suggest that the functional group affects the electron-donating ability of the COFs, which successively impacts the charge transfer between COFs and Pd sites, giving rise to a modulated Pd electronic state and excellent catalytic performance.     

Photo-Induced Switching of CO2 Hydrogenation Pathway towards CH3OH Production over Pt@UiO-66-NH2(Co)

It is highly desired to achieve controllable product selectivity in CO₂ hydrogenation. Herein, we report light-induced switching of reaction pathways of CO₂ hydrogenation towards CH₃OH production over actomically dispersed Co decorated Pt@UiO-66-NH₂. CO, being the main product in the reverse water gas shift (RWGS) pathway under thermocatalysis condition, is switched to CH₃OH via the formate pathway with the assistance of light irradiation. Impressively, the space-time yield of CH₃OH in photo-assisted thermocatalysis (1916.3 μmol g_cat⁻¹ h⁻¹) is about 7.8 times higher than that without light at 240 °C and 1.5 MPa. Mechanism investigation indicates that upon light irradiation, excited UiO-66-NH₂ can transfer electrons to Pt nanoparticles and Co sites, which can efficiently catalyze the critical elementary steps (i.e., CO₂-to-*HCOO conversion), thus suppressing the RWGS pathway to achieve a high CH₃OH selectivity.     

Controlled Partial Linker Thermolysis in Metal-Organic Framework UiO-66-NH2 to Give a Single-Site Copper Photocatalyst for the Functionalization of Terminal Alkynes

Metal–organic frameworks (MOFs) with expanding porosity and tailored pore environments are intriguing for catalytic applications. We report herein a straightforward method of controlled partial linker thermolysis to introduce desirable mesopores into mono-ligand MOFs, which is different from the classical thermolyzing method that starts from mixed-linker MOFs. UiO-66-NH₂, after partial ligand thermolysis, exhibits significant mesoporosity, retained crystal structure, improved charge photogeneration and abundant anchoring sites, which is ideal to explore single-site photocatalysis. Atomically dispersed Cu is then accommodated in the tailored pore. The resulting single-site Cu catalyst exhibits excellent performance for photocatalytic alkylation and oxidation coupling for the functionalization of terminal alkynes. The study highlights the advantage of controlled partial linker thermolysis to synthesize hierarchical MOFs to achieve the advanced single-site photocatalysis.     

Identifying the Role of Lewis-base Sites for the Chemistry in Lithium-Oxygen Batteries

Lewis-base sites have been widely applied to regulate the properties of Lewis-acid sites in electrocatalysts for achieving a drastic technological leap of lithium-oxygen batteries (LOBs). Whereas, the direct role and underlying mechanism of Lewis-base in the chemistry for LOBs are still rarely elucidated. Herein, we comprehensively shed light on the pivotal mechanism of Lewis-base sites in promoting the electrocatalytic reaction processes of LOBs by constructing the metal–organic framework containing Lewis-base sites (named as UIO-66-NH₂). The density functional theory (DFT) calculations demonstrate the Lewis-base sites can act as electron donors that boost the activation of O₂/Li₂O₂ during the discharged-charged process, resulting in the accelerated reaction kinetics of LOBs. More importantly, the in situ Fourier transform infrared spectra and DFT calculations firstly demonstrate the Lewis-base sites can convert Li₂O₂ growth mechanism from surface-adsorption growth to solvation-mediated growth due to the capture of Li⁺ by Lewis-base sites upon discharged process, which weakens the adsorption energy of UIO-66-NH₂ towards LiO₂. As a proof of concept, LOB based on UIO-66-NH₂ can achieve a high discharge specific capacity (12 661 mAh g⁻¹), low discharged-charged overpotential (0.87 V) and long cycling life (169 cycles). This work reveals the direct role of Lewis-base sites, which can guide the design of electrocatalysts featuring Lewis-acid/base dual centers for LOBs.     

NMR approach for the identification of dinuclear and mononuclear complexes: The first detection of [Pd(SPh)2(PPh3)2] and [Pd2(SPh)4(PPh3)2] - The intermediate complexes in the catalytic carbon-sulfur bond formation reaction

In the present study we have analyzed the nature of palladium complexes in the catalytic system for selective carbon-sulfur bond formation via the addition of S-S and S-H bonds to alkynes. For the first time the mononuclear and dinuclear palladium complexes were clearly detected by DOSY NMR under the catalytic conditions. It was demonstrated that the concentration of these palladium complexes strongly depends on the amount of phosphine ligand available under reaction conditions.     

CO2 Hydrogenation over Oxide‐Supported PtCo Catalysts: The Role of the Oxide Support in Determining the Product Selectivity

By simply changing the oxide support, the selectivity of a metal–oxide catalysts can be tuned. For the CO₂ hydrogenation over PtCo bimetallic catalysts supported on different reducible oxides (CeO₂, ZrO₂, and TiO₂), replacing a TiO₂ support by CeO₂ or ZrO₂ selectively strengthens the binding of C,O‐bound and O‐bound species at the PtCo–oxide interface, leading to a different product selectivity. These results reveal mechanistic insights into how the catalytic performance of metal–oxide catalysts can be fine‐tuned.