Fabrication of porous boron-doped diamond electrodes by catalytic etching under hydrogen–argon plasma

Abstract

Porous boron-doped diamond (BDD) was prepared by hydrogen–argon plasma etching using electrodeposited Ni nanoparticles as a catalyst. The etching process and formation mechanism of porous BDD were investigated by changing the etching time from 30s to 300s. Pores were produced due to the C atoms around Ni nanoparticles are easy to react with hydrogen plasma and form methane. With the increase of etching time, the pore size increased, the pore density decreased, and the pore depth first increased and then maintained unchanged. The sp2-bonded graphitic carbons existing on the surface of BDD increase with increasing etching time due to the increase of surface area. No preferential etching was observed due to the high energy of argon plasma. The electrochemical behaviors of the pristine and porous BDD electrodes were characterized by cyclic voltammetry (CV), galvanostatic charge–discharge (GCD) and electrochemical impedance spectroscopy (EIS). The results showed that the porous BDD electrode exhibited high specific capacitance, which is attributed to its high electrical conductivity and large specific surface area. The highest specific capacitance of porous BDD electrode is 9.55mFcm−2, which is 22 times higher than that of pristine BDD electrode. The specific capacitance retention of the porous BDD electrode reduced to 98.2% of the initial capacitance after 500 cycles and then increased to 120.0% after 10,000 cycles. For the first 500 cycles, the reduction of capacitance can be attributed to the dissolution of Ni nanoparticles that attached on the porous BDD surface or buried in the shallow layer. The capacitance increase after 10,000 cycles is due to the better contact of the electrolytic solution with the residual Ni with the increase of cycle number.