Development of non-noble metal catalysts with similar activity and stability to noble metals is of significant importance in the conversion and utilization of clean energy. The catalytic hydrolysis of ammonia borane (AB) to produce 3 equiv. of H₂, as an example of where noble metal catalysts significantly outperform their non-noble peers, serves as an excellent test site for the design and optimization of non-noble metal catalysts. Our kinetic isotopic effect measurements reveal, for the first time, that the kinetic key step of the hydrolysis is the activation of H₂O. Deducibly, a transition metal with an optimal electronic structure that bonds H₂O and –OH in intermediate strengths would favor the hydrolysis of AB. By employing a covalent triazine framework (CTF), a newly developed porous material capable of donating electrons through the lone pairs on N, the electron densities of nano-sized Co and Ni supported on CTF are markedly increased, as well as their catalytic activities. Specifically, Co/CTF exhibits a total turnover frequency of 42.3 mol H₂ mol_Co ⁻¹ min⁻¹ at room temperature, which is superior to all peer non-noble metal catalysts ever reported and even comparable to some noble metal catalysts.

Light harvesting, separation of charge carriers, and surface reactions are three fundamental steps that are essential for an efficient photocatalyst. Here we show that these steps in the TiO₂ can be boosted simultaneously by disorder engineering. A solid-state reduction reaction between sodium and TiO₂ forms a core-shell c-TiO₂@a-TiO_2-x(OH)_y heterostructure, comprised of HO-Ti-[O]-Ti surface frustrated Lewis pairs (SFLPs) embedded in an amorphous shell surrounding a crystalline core, which enables a new genre of chemical reactivity. Specifically, these SFLPs heterolytically dissociate dihydrogen at room temperature to form charge-balancing protonated hydroxyl groups and hydrides at unsaturated titanium surface sites, which display high reactivity towards CO₂ reduction. This crystalline-amorphous heterostructure also boosts light absorption, charge carrier separation and transfer to SFLPs, while prolonged carrier lifetimes and photothermal heat generation further enhance reactivity. The collective results of this study motivate a general approach for catalytically generating sustainable chemicals and fuels through engineered disorder in heterogeneous CO₂ photocatalysts.

A covalent triazine framework (CTF) with high surface area, large amount of nitrogen functionalities, and high porosity and basicity was employed as a support for palladium nanoparticles (NPs). A well-dispersed Pd/CTF-1 catalyst with uniform distribution of Pd particles was successfully synthesized in the present study. The as-prepared 4% Pd/CTF-1 catalyst showed a markedly improved activity in the hydrogenation of N-heterocyclic compounds compared to the activated carbon (AC)-supported catalyst, i.e., the Pd/CTF-1 catalyst exhibits ca. 3.6 times faster reaction than Pd/AC in the hydrogenation of N-methylpyrrole. Characterization of Pd/CTF indicated electron donation from the N in CTF to the metallic Pd NPs, showing intensified electronic interaction between the Pd NPs and CTF support, which is responsible for the enhanced activities for the catalytic hydrogenation of N-heterocycles.