High faradaic efficiencies can be achieved in the production of formic acid (HCOOH) by metal electrodes, such as Sn or Pb, in the electrochemical reduction of carbon dioxide (CO ). However, the stability and environmental load in using them are problematic. The electrochemical reduction of CO to HCOOH was investigated in a flow cell using boron-doped diamond (BDD) electrodes. BDD electrodes have superior electrochemical properties to metal electrodes, and, moreover, are highly durable. The faradaic efficiency for the production of HCOOH was as high as 94.7 %. Furthermore, the selectivity for the production of HCOOH was more than 99 %. The rate of the production was increased to 473 μmol m s at a current density of 15 mA cm with a faradaic efficiency of 61 %. The faradaic efficiency and the production rate are almost the same as or larger than those achieved using Sn and Pb electrodes. Furthermore, the stability of the BDD electrodes was confirmed by 24 h operation.

Boron-doped diamond (BDD) has attracted much attention as a promising electrode material especially for electrochemical sensing systems, because it has excellent properties such as a wide potential window and low background current. It is known that the electrochemical properties of BDD electrodes are very sensitive to the surface termination such as to whether it is hydrogen- or oxygen-terminated. Pretreating BDD electrodes by cathodic reduction (CR) to hydrogenate the surface has been widely used to achieve high sensitivity. However, little is known about the effects of the CR treatment conditions on surface hydrogenation. In this Article, we report on a systematic study of CR treatments that can achieve effective surface hydrogenation. As a result, we found that the surface hydrogenation could be improved by applying a more negative potential in a lower pH solution. This is because hydrogen atoms generated from protons in the CR treatment contribute to the surface hydrogenation. After CR treatments, BDD surface could be hydrogenated not completely but sufficiently to achieve high sensitivity for electrochemical sensing. In addition, we confirmed that hydrogenation with high repeatability could be achieved.

The main product obtained by electrochemical reduction of CO2 depends on the electrode material, and in many cases the Faradaic efficiency for this is determined by the electrolyte. Only a few investigations in which attempts to produce different products from the same electrode material have been done so far. In this work, we focus on boron-doped diamond (BDD) electrodes with which plentiful amounts of formic acid and small amounts of carbon monoxide have been produced. By optimizing certain parameters and conditions used in the electrochemical process with BDD electrodes, such as the electrolyte, the boron concentration of the BDD electrode, and the applied potential, we were able to control the selectivity and efficiency with which carbon monoxide is produced. On one hand, with a BDD electrode with 1% boron used for the cathode and KClO4 for the catholyte, the selectivity for producing carbon monoxide was high. On the other hand, with a BDD electrode with 0.1% boron used for the cathode and KCl for the catholyte, the production of formic acid was the most evident. In situ attenuated total reflectance-infrared (ATR-IR) measurements during electrolysis showed that CO2 •– intermediates were adsorbed on the BDD surface in the KClO4 aqueous solution. Here, switchable product selectivity was achieved when reducing CO2 using BDD electrodes.

Direct evidence: The existence of methoxy radical species formed during an anodic oxidation in MeOH on a boron‐doped diamond (BDD) electrode was confirmed by ESR spectroscopy. Effective production of a neolignan, licarin A, was accomplished by the BDD‐mediated anodic oxidation protocol (see picture).

The long-term durability of boron-doped diamond electrodes (BDD) used continuously in the electrochemical conversion of CO 2 to formic acid was investigated. Although the Faradaic efficiency (FE) for the production of formic acid decreased with increasing electrolysis time, the FE was easily recovered by electrochemical oxidation of the BDD electrodes in H 2 SO 4 , Na 2 SO 4 or K 2 SO 4 solutions. For practical application, the long-term production of formic acid using BDD electrodes can be successfully accomplished just by successive polarity reversal of plus and minus terminals. Furthermore, at a current density of −20 mA cm −2 , the rate of production reached 328 μmol h −1 cm −2 , which is the highest value ever obtained using plate electrodes. Consequently, we found that BDD electrodes are ideal for industrial application of CO 2 reduction.

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Rb+ cations provide a greater effect on the electrochemical conversion of CO2 to formic acid using BDD electrodes.

The electrochemical reduction of CO2 was investigated in an aqueous ammonia solution using boron-doped diamond electrodes.