Covalent triazine framework supported non-noble metal nanoparticles with superior activity for catalytic hydrolysis of ammonia borane: from mechanistic study to catalyst design

摘要

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.