Surface Reconstruction for Selective Oxidation of Tetrahydroisoquinoline.

Integration of hydrogen evolution with the oxidation of organic substances in one electrochemical system is highly desirable. However, achieving selective oxidation of organic substances in the integrated system is still highly challenging. In this study, a phosphorylated NiMoO4 nanoneedle-like array was designed as the catalytic active electrode for the integration of highly selective electrochemical dehydrogenation of tetrahydroisoquinolines (THIQs) with hydrogen production. The leaching of anions, including MoO42- and PO43-, facilitates the reconstruction of the catalyst. As a result, nickel oxyhydroxides with the doping of PO43- and richness of defects are in situ formed. In situ Raman and density functional theory calculations have shown that the high catalytic activity is attributed to the in situ formed PO43- involved NiOOH substance. In the dehydrogenation process, the involved C-H bond but not the N-H bond is first destroyed. A two-electrode system was then fabricated with the optimized electrode that shows a benchmark current density of 10 mA cm-2 at 1.783 V, providing a yield of 70% for dihydroisoquinolines. A robust stability was also shown for this integrated electrochemical system. The understanding of the reconstruction behavior and the achievement of selective dehydrogenation will provide some hints for electrochemical synthesis.

Branched Porous Ni3N as a Catalytic Electrode for Selective Semidehydrogenation of Tetrahydroisoquinoline.

Oxygen evolution in electrochemical water splitting needs a high overpotential that significantly reduces the energy efficiency. To explore an alternative anodic reaction to promote the production of hydrogen at the other end of water splitting and at the same time to get high-value-added chemicals is highly desirable. Herein, we demonstrate a novel branched porous Ni3N catalyst that is prepared for dehydrogenation of tetrahydroisoquinoline, which acts as an anodic oxidation reaction to promote H2 formation on the other end. Interestingly, the Ni3N catalytic electrode can induce effective semidehydrogenation with the selective formation of dihydroisoquinoline, which is difficult to be obtained by the usual direct synthesis route. The catalytic electrode exhibits a low potential of 1.55 V (vs RHE) for a catalytic current density of 61 mA cm-2 with dehydrogenation of tetrahydroisoquinoline and hydrogen production. In situ Raman spectra studies suggest that NiOOH is formed on the electrode surface, which mediates the oxidation semidehydrogenation process. This work also provides a strategy to fabricate nitride materials for applications beyond selective semidehydrogenation of tetrahydroisoquinoline.