Facile and controllable preparation of carbon microsphere for electro-driven nitrogen reduction: Accommodating nitrogen doping with hierarchical porous structure.

Driven by sustainable electricity, electrochemical nitrogen fixation under ambient conditions is considered as a promising strategy to generate low-concentrated NH3/NH4+. Under the principle of doping and porous engineering, nitrogen-doped carbon microsphere with hierarchical pores (NC-HP) is fabricated via pyrolyzing polymer microsphere. Hierarchical structure with macro-, meso- and micropores is obtained by assembling melamine/phenol-formaldehyde oligomers in Pickering droplets, with the assistance of triblock copolymer Pluronic F127. The regularity of mesopores is strongly affected by melamine to phenol mass ratio. For NC-HP, nitrogen content (N-content) in the carbon matrix can reach as high as 19.1 wt%, yet trade-off effect is observed between N-content and regularity of mesopores. As consequence, NC-HP-3 with N-content of 15.6 wt% and distinct mesopores exhibits the highest catalytic performance. At -0.5 V vs. RHE, NH3/NH4+ production rate and Faradaic efficiency (FE) value reach 15.6 μg∙mgcat.-1∙h-1 and 15.5%, respectively. It shows excellent recyclability, and no degradations are observed with respect to morphology and porous structure. In this hierarchical porous structure, mesopores are expected to facilitate mass transfer for both electrolyte ions and nitrogen, and hence catalytic active sites (e.g. pyrrolic- and pyridinic-N species) in hierarchically mutually connected pores can be well utilized.