The deep hydrogenation of aromatic rings remains challenging due to their inherent stability and low hydrogen solubility in solvents. Addressing both kinetic limitations and gas–liquid–solid mass transfer resistance under mild conditions requires innovative catalyst design. Herein, we address this hurdle by developing “hydrogen pumping catalysts” featuring ultrafine Rh nanoclusters within CAS-1, a novel potassium calcium silicate material (Ca₄K₄(H₂O)₈Si₁₆O₃₈). The outstanding advantage of the RhCAS-1 catalyst lies in its superior hydrogen storage capability, which ensures an uninterrupted hydrogen provision to catalytic active sites. Operating at ambient temperature, RhCAS-1 enables fully saturated hydrogenation of polycyclic aromatic hydrocarbons (e.g., naphthalene, toluene, and anthracene) with high conversion efficiency, while maintaining high catalytic stability over 20 consecutive operational cycles without detectable degradation. These findings establish a multifunctional framework for heterogeneous catalyst design that seamlessly integrates H₂ storage and activation, enabling energy-efficient hydrogenation of aromatic compounds.

Pt-WO_x-based catalysts, known for their bifunctional nature, have shown promise in selective hydrodeoxygenation (HDO) reactions. Gaining insights into the activation process of H₂ and the origin of Brønsted acidity on Pt-WO_x sites is essential for enhancing reaction performance. In this work, we have developed a methodology to meticulously regulate the domain size of WO_x species on SBA-15 supported by utilizing the in-situ hydrolysis of WCl₆ with the hydroxyl groups on SBA-15. This approach allowed us to achieve different polymeric degrees of WO_x species on SBA-15. Notably, the low polymeric WO_x species associated with Pt, demonstrated significantly augmented catalytic activity in glycerol hydrogenolysis to 1,3-propanediol. The adsorption and activation of H₂ on such catalysts were systematically examined using in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). It was found that the Pt-WO_x interface facilitates the heterogeneous dissociation of H₂, generating hydride species (W-OH^δ+) that act as Brønsted acid sites, thereby enhancing catalytic activity. Our findings offer a new perspective on understanding the HDO reaction mechanism and provide valuable insights for the development of highly efficient catalysts for such reactions.

The chemoselective hydrogenation of α,β-unsaturated aldehydes is a key strategy for the synthesis of fine chemicals. Herein, we developed an efficient method of depositing Pt particles on FeO_x/SBA-15. This strategy is dependent on using a platinum-divinyltetramethyldisiloxane complex (Pt⁰-DVTMS) as the precursor, which we demonstrate can be removed through a H₂-treatment under mild conditions. This, in turn, allowed for the synthesis of catalysts with well dispersed Pt particles. The presence of FeO_x species also aided Pt dispersion; when coated onto SBA-15, FeO_x strongly interacted with dissociated Pt species, inhibiting both Pt aggregation and metal leaching. Using cinnamaldehyde as a model α,β-unsaturated aldehyde, it was demonstrated that this catalyst was highly selective towards the unsaturated alcohol and no obvious loss in activity was observed over five recycles. This catalyst was determined to be significantly more effective than an analogous catalyst prepared using chloroplatinic acid as a precursor, evidencing the importance of using the Pt⁰-DVTMS precursor. We corroborate the excellent catalytic performance to highly dispersed Pt-species, whereby Pt⁰ and Pt²⁺ play a critical role in activating H₂ and the C=O bond. This research demonstrates that the Pt precursor can have a significant impact on the physicochemical properties and thus, the performance of the final catalyst. It also evidences how metal support interactions can dramatically influence selectivity in such hydrogenation reactions. This novel catalyst preparation protocol, using a DVTMS ligand for Pt impregnation, offers a facile approach to the design of multi-component heterogeneous catalysts.