Boron-Doped Diamond Electrodes: Fundamentals for Electrochemical Applications

Boron-doped diamond (BDD) electrodes have emerged as next-generation electrode materials for various applications in electrochemistry such as electrochemical sensors, electrochemical organic synthesis, CO₂ reduction, ozone water generation, electrochemiluminescence, etc. An optimal BDD electrode design is necessary to realize these applications. The electrochemical properties of BDD electrodes are determined by important parameters such as (1) surface termination, (2) surface orientation, and (3) boron doping level.In this Account, we discuss how these parameters contribute to the function of BDD electrodes. First, control of the surface termination (hydrogen/oxygen) is described. The electrochemical conditions such as the solution pH and the application potential were studied precisely. It was confirmed that an acidic solution and the application of negative potential accelerate hydrogenation, and the mechanism behind this is discussed. For oxygenation, we directly observed changes in surface functional groups by in situ attenuated total reflection infrared spectroscopy and electrochemical X-ray photoelectron spectroscopy measurements.Next, the difference in surface orientation was examined. We prepared homoepitaxial single-crystal diamond electrodes comprising (100) and (111) facets with similar boron concentrations and resistivities and evaluated their electrochemical properties. Experimental results and theoretical calculations revealed that (100)-oriented single-crystal BDD has a wider space charge layer than (111)-oriented BDD, resulting in a slower response. Furthermore, isolated single-crystal microparticles of BDD with exposed (100) and (111) crystal facets were grown, and we studied the electrochemical properties of the respective facets by combination with hopping-mode scanning electrochemical cell microscopy.We also systematically investigated how the boron concentration and sp² species affect the electrochemical properties. The results showed that the appropriate composition (boron and sp² species level) is dependent on the application. The transmission electron microscopy images and electron energy loss spectra of highly boron-doped BDD are shown, and the relationship between the composition and electrochemical properties is discussed. Finally, we investigated in detail the effect of the sp² component on low-doped BDD. Surprisingly, although the sp² component is usually expected to induce a narrowing of the potential window and an increase in the charging current, low-doped BDD showed the opposite trend depending on the degree of sp² carbon.The results and discussion presented in this Account will hopefully promote a better understanding of the fundamentals of BDD electrodes and be useful for the optimal development of electrodes for future applications.