Document type: Review/Account

Award Account

Development of Electrochemical Applications of

Boron-Doped Diamond Electrodes

Yasuaki Einaga

Department of Chemistry, Keio University, 3-14-1 Hiyoshi, Yokohama, Kanagawa 223-8522, Japan
E-mail: [email protected]

Received: September 7, 2018; Accepted: September 22, 2018; Web Released: October 6, 2018

Yasuaki Einaga
Yasuaki Einaga is a professor in the Department of Chemistry at Keio University, Japan. He received his BS
(1994), MS (1996), and PhD (1999) from The University of Tokyo. After 2 years as a research associate at
The University of Tokyo, he started his faculty career as an assistant professor at Keio University in 2001. He
was promoted to associate professor in 2003, and to professor in 2011. He has also been a research director
of JST-CREST (2011–2014), and JST-ACCEL (2014–present). His research interests include functional
materials science, photochemistry, electrochemistry, and diamond electrodes.

Abstract present, there are electrodes and systems used for wastewater
It is well known that “diamond” has ultra-high hardness and treatment, and ozone generation systems are partly commer-
low electrical conductivity. However, introducing dopants such cially available, while other applications are still at the funda-
as boron into the diamond lattice during growth can increase its mental research stage. However, prototypes of a number of dif-
conductivity. Boron-doped diamond (BDD) with high con- ferent electroanalytical devices have been produced by several
ductivity is attracting increasing attention as one of the next- companies. This means that these electroanalytical devices are
generation of superior electrode materials. In particular, it is almost in practical use.
expected that BDD electrodes can help solve some of our More recently, electrochemical synthesis and electrocatalysis
environmental problems and also improve our quality of life have also been very much highlighted.10,11 For a future sustain-
through their use in biomedical devices. Here, in this article, able society, materials scientists are encouraged to create inno-
recent developments in the electrochemical applications of vative functions for intelligent materials that are quite different
boron-doped diamond (BDD) electrodes are introduced. from conventional functions, based on the concept of the
Element Strategy, “understanding and effective use of the roles
Keywords: Boron-doped diamond j Electrochemistry j of key elements that determine the properties and functions of
Electrode materials intelligent materials”. BDD, which is carbon-based, is a strate-
gically important material from this point of view. Moreover,
the number of publications involving BDD electrochemistry
1. Introduction research has been rapidly increasing year by year. Several
Doping diamond with boron increases its conductivity. The review articles and books on diamond electrodes have been
conductivity is controlled by the doping level, and the diamond published.12­14 Here, in this article, we introduce recent devel-
can range from an insulator to a metal-like conductor, or opments made in the electrochemical applications of boron-
behave as a superconductor at low temperature. Especially, doped diamond (BDD) electrodes.
relatively high boron-doped (103­104 ppm) diamond that has
metal-like conductivity can be used as an electrode material. 2. Boron-Doped Diamond (BDD) Electrodes
These days, highly conducting boron-doped diamond (BDD) 2.1 Typical Method for the Preparation of BDD Elec-
electrodes are widely used in a number of different electro- trodes. BDD electrodes can be deposited on Si (100) wafers
chemical applications.1­9 Two of the most popular applications in a microwave plasma-assisted chemical vapor deposition
are wastewater treatment and electrochemical analysis. From (CVD) system. The source gases are introduced into the reactor
the viewpoint of the practical application of these electrodes, at by bubbling hydrogen gas through a liquid mixture of acetone

1752 | Bull. Chem. Soc. Jpn. 2018, 91, 1752–1762 | doi:10.1246/bcsj.20180268 © 2018 The Chemical Society of Japan
 (a)

Au

-1 0 1 2
Potential (V vs. Ag/AgCl)

Figure 1. Potential windows of various electrodes.

(b)
and trimethoxyborane (B(OCH3)3). The liquid can be prepared
with appropriate mixing ratios based on Raoult’s law so that
the boron/carbon (B/C) ratios in the reactor can be controlled.
The typical grain size of the resulting BDD films is up to
³5 ¯m, with a thickness of ³20 ¯m for deposition times of 7 h
using 5 kW of plasma power.
2.2 Electrochemical Properties of BDD as an Electrode
Material. The potential stability window of water with BDD
electrodes is extremely wide, and the background current is
low (Figure 1). Moreover, these electrodes have good chemi-
cal and mechanical stability, are resistant to fouling, have no
surface oxide, and their surface termination can be controlled.
These characteristics have led to the application of BDD elec-
trodes in electrochemical sensing, in electroanalysis, in electro-
chemical synthesis, and for the anodic treatment of organic Figure 2. (a) Linear Sweep Voltammograms (LSVs) for 1.4
waste. BDD can also be used as a transparent, conducting mM free chlorine in 0.1 M NaClO4 with different pH and
medium for analytical chemistry and photoelectrochemical LSVs in the absence of free chlorine in 0.1 M NaClO4 at
applications. a scan rate of 20 mV/s using a BDD electrode. (b) The pH
dependence of the peak current in the first reduction waves
3. Electrochemical Sensor Applications of the LSVs and the ratio of HClO to HClO plus ClO¹ in
equilibrium. (Reproduced with permission from ref. 17).
3.1 Development of a Free Chlorine Sensor. In 2008, we
reported on utilizing the oxidation reaction for the electrochem-
ical detection of free chlorine using BDD electrodes.15 In that clearly corresponds to the level of HClO. The following
paper, the oxidation of free chlorine could be observed due to scheme for HClO reduction was proposed.18
the wide potential window of BDD, whereas with other elec- HClO þ e ! HClO ðadsÞ ð1Þ
trodes the evolution of oxygen interfered with the measure-   
ments. However, compensation for the pH dependence is also 2HClO ðadsÞ ! Cl þ ClO þ H2 O ð2Þ
necessary with BDD electrodes in order to determine the total On the other hand, the second reduction wave seems to have
free chlorine because, as with other electrodes, it is only ClO¹ no relation with pH. This means that ClO¹ can also be reduced
that can be oxidized.16 On the other hand, there had been no in the second wave while the oxygen reduction reaction (ORR),
reports on the electrochemical reduction of free chlorine at which is observed even in the absence of free chlorine, occurs
BDD electrodes. Thus, we examined the electrochemical reduc- at this potential. The peak current in the first wave increases in
tion behavior of free chlorine (HClO and ClO¹).17 proportion to the concentration of HClO. That is, for analytical
Figure 2a shows linear sweep voltammograms (LSVs) of purposes, the first wave for HClO reduction should be advan-
1.4 mM free chlorine in 0.1 M NaClO4 (non-degassed) with tageous due to the high selectivity against ORR. However, for
different pH from 5 to 9 using a BDD electrode. For the LSVs drinking water analysis the concentration range is around 0­
in the presence of free chlorine, the BDD exhibits two reduc- 5 mg/L (0­70 ¯mol/L),19 which is approximately 100 times
tion waves at around ¹0.4 V and ¹1.3 V. Regarding the first lower than the present conditions. The limit of detection (LOD)
reduction wave, the peak current decreases with increasing pH defined as the concentration corresponding to 3σ, where σ is the
and almost disappears at pH 9. Figure 2b shows the pH depen- standard deviation of the LSV background current, was esti-
dence of the peak current at the potential at which the peak or mated to be 98 mg/L. The relative standard deviation (RSD)
minimum «dI/dV« in the first wave occurs. The ratio of HClO of the peak current for the LSV with pretreatment was 0.45%.
to total free chlorine, which can be determined from pKa, is Considering that there is room for improvement in the measure-
also displayed in Figure 2b. The value of the reduction current ment technique, these values for LOD and RSD are promising.

Bull. Chem. Soc. Jpn. 2018, 91, 1752–1762 | doi:10.1246/bcsj.20180268 © 2018 The Chemical Society of Japan | 1753
 BDD microelectrode
Counter electrode 0.20
Stimulating electrode (c)

Current / nA
(b) 0.18

0.16
Anesthesia 0.14
induction 5.0
(a) 0.12
0.8 0.9 1.0 1.1
Reference

Current / nA
Potential / V vs Ag/AgCl
electrode
4.8

4.6

200 400 600 800 1000

Time / sec

Figure 3. (a) SEM image of BDD microelectrode. (b) Photo of in vivo mouse brain experimental set up. (c) Differential pulse
voltammetry (DPV) monitoring the current response following MFB stimulation (50 Hz, 100 pulses for 2 sec) measured at an
applied potential of 0.9 V (vs. Ag/AgCl) with an ao-BDD microelectrode. The inset in (c) shows the dependence of the signal
current on the applied potential. DPV setting; frequency 50 Hz, potential step 100 mV, pulse amplitude 150 mV, starting potential
0.65 V vs. Ag/AgCl. (Reproduced with permission from ref. 20).

On the other hand, with BDD electrodes, the reduction of ClO¹ was used as a model analyte. This drug is used for the treatment
is not suitable for analytical purposes because of the dissolved of hypertension, oedema and ascites29 and has been tested for
oxygen. Alternatively, considering the complementary behav- suppression of infantile epilepsy; however, it has adverse side
ior of the oxidation reaction,15 the total concentration of free effects such as deafness and hypokalaemia.
chlorine can be determined by combining both reactions. A BDD microelectrode and a double-barreled reference
3.2 A Microsensing System for In Vivo Real-Time electrode were inserted into the perilymph in the scala tympani,
Detection of Local Drug Kinetics and Its Physiological a compartment in the cochlea (cross-sectional area of the scala
Relevance. In 2007, we reported the first example of an tympani: ³1.5 mm2). Furthermore, a glass microelectrode was
in vivo sensor using a BDD microelectrode. The BDD micro- inserted in the scala media, which is a neighboring chamber
electrode was inserted into the striatum in a mouse brain,20 and containing a K+-rich (150 mM) extracellular fluid®the endo-
electrical stimulation to the medial forebrain bundle (MFB) lymph. Under physiological conditions the electrical potential
was applied to induce dopamine (DA) release. Figure 3 shows between the endolymph and the perilymph is strongly positive
the signal response following stimulation. A clear signal was (³ +80 mV) and this endocochlear potential (EP) is crucial for
recorded for each stimulation and indicated that in vivo hearing.30 Since the EP value is correlated with the hearing
monitoring of DA was successfully achieved using the BDD level, the animal is severely deaf when the EP is negative. The
microelectrode. function of the cochlea can then be directly assessed by mea-
Following that report, BDD microelectrodes have received a suring the EP with a glass microelectrode in the scala media
great deal of attention as an electrochemical sensor, especially (Figure 4a).
as an in vivo sensor.21­24 The concentration of bumetanide was monitored by a BDD
In 2017, we succeeded in realizing real time recording of the microelectrode every 5 seconds. An intravenous injection of
kinetics of systemically administered drugs in vivo.25 Real time bumetanide (30 mg kg¹1 bodyweight in 1 ml PBS) was per-
recording of administered drugs can accelerate the development formed after 30 min. About 45 seconds after the injection, the
of effective medical therapies. It is difficult to accomplish this BDD-microsensor current began to rise and peaked at 13.6 nA
by conventional methods because they require large quantities (corresponding to 5.3 ¯M) after about 75 seconds. The current
of analyte and the sampling rates are low. Thus, we have then gradually declined and returned almost to the initial level
developed a novel system comprising a BDD microelectrode 5 minutes after injection.
with a tip diameter of ³40 ¯m, which monitors the concen- The evolution of the EP showed a different time course, as
tration of the drug, and a glass microelectrode, which monitors displayed in Figure 4b. The onset of the response began around
the physiological phenomena by obtaining extra- or intra- 35 s after that of the BDD microsensor.
cellular electrical parameters resulting from ion-channel and/or As another example, when doxorubicin was injected, the
ion-transporter activity.26 At first, bumetanide, a diuretic that is current (concentration of doxorubicin) reached a maximum at
ototoxic but applicable to epilepsy treatment, was examined. In about 3 minutes after injection. However, little change was
the guinea-pig cochlea, changes in bumetanide concentration detected in the simultaneously recorded EP. This is consistent
and the endocochlear potential underlying hearing were simul- with there being no reports in the literature of an association
taneously measured in real time. between doxorubicin and hearing impairment.
Bunetanide, a loop diuretic that blocks the Na+­K+­2Cl¹ Furthermore, the relationship between the action of lamo-
cotransporter expressed in the kidney, brain and cochlea,27,28 trigine (antiepileptic drug) and neuronal activity was also

1754 | Bull. Chem. Soc. Jpn. 2018, 91, 1752–1762 | doi:10.1246/bcsj.20180268 © 2018 The Chemical Society of Japan
 (a) radicals and the electrode surface is weak. Therefore, the
hydroxyl radicals are physically adsorbed on the electrode sur-
face, and the oxidation of the organic compounds is mediated
by the hydroxyl radicals (5). In fact, in a competitive reaction,
the hydroxyl radicals generate oxygen without any participa-
tion of the electrode (6).
Mð•OHÞ þ R ! M þ mCO2 þ nH2 O þ e ð5Þ
þ 
Mð•OHÞ ! M þ 1=2O2 þ H þ e ð6Þ
(b)
The properties of hydroxyl radicals generated using BDD
electrode have been widely applied to the treatment of waste-
water. Not only the direct generation of hydroxyl radicals, but
also further reactions have occurred, i.e., the formation of
persulfate,38,39 perphosphate, percarbonate,40 and hypochlor-
ite,41­43 which can also be used for wastewater treatment. The
synthesis of ferrates and ozonated water,44­46 and aromatic
hydroxylation mediated by OH radicals have also been report-
ed.47 On the other hand, it is suggested that these properties can
Figure 4. (a) A BDD microsensor for the detection of be applied to the development of organic electrochemical
bumetanide was inserted into the perilymph of the scala reactions via “active species” such as radicals.
tympani (ST) of the guinea pig cochlea, and a double- 4.1 Electrochemical Synthesis via Methoxy Radicals. In
barreled glass microcapillary encasing a reference (RE; 2004, Comninellis et al. reported the first example of an
Ag/AgCl) and counter electrode (CE; platinum) was placed electrochemical reaction via methoxy radicals generated from
in close proximity. The EP was simultaneously monitored methanol by an anodic reaction using BDD electrodes. Anodic
using a glass microelectrode in the endolymph of the scala oxidation of 1,2-diphenyl-ethanes in CH3OH-H2SO4-H2O
media (SM). SV, scala vestibule; StV; stria vascularis. solution produced p-tert-butylbenzaldehyde dimethyl acetal
(b) In vivo measurements in a guinea pig cochlea using the (TBAL) via carbon-carbon bond cleavage due to the formation
microsensor electrode. The BDD-microsensor subtraction of methoxyl radicals.48 Furthermore, they also reported the
current (SC; green) in the perilymph of the scala tympani production of trimethylorthoformate (TMOF) by anodic oxi-
and the EP (red) measured with a microelectrode in the dation of formaldehyde dimethylacetal (FADMA) in a solu-
endolymph of the scala media are shown. (Reproduced with tion containing methanol using a BDD electrode.49 In 2014, we
permission from ref. 25).
confirmed the generation of methoxy radicals with a BDD
studied. Microsensing systems offer the potential to detect electrode by ESR.50 Anodic oxidation of methanol containing
pharmacological and physiological responses that cannot be 0.1 M LiClO4 and 10 mM DMPO (radical trapping agent: 5,5-
detected by other means, and, moreover, it is possible to apply dimethyl-1-pyrroline-N-oxide) was performed with a BDD
them to other organs and to other drugs. electrode at a constant potential of +1.6 V (vs. Ag/AgCl). The
ESR signal of the product showed the magnetic field value
4. Electrochemical Organic Synthesis anticipated for nitroxyl radicals, which were generated by the
Electrochemical organic synthesis is considered to be a reaction of the methoxyl radicals with DMPO (Figure 5).50 The
“green” technology, because only electrons are used as reagents ESR signals for these radicals produced in similar experi-
and almost no waste reagent is produced.31 For normal molec- ments using both glassy carbon and Pt electrodes were of lower
ular transformation, oxidation or reduction with a metal catalyst intensity, indicating that BDD electrodes are more effective
is necessary. On the other hand, oxidation/reduction free and than glassy carbon or Pt electrodes in producing methoxyl
catalyst free molecular transformation are possible in electro- radicals. Furthermore, electrochemical oxidation of isoeugenol
chemical syntheses by precise adjustment of the electrochem- (1) using BDD electrodes produced the benzofuran-type neo-
ical parameters, such as the redox potential, the current density, lignan, 3 (lycarin A), 5 as a result of coupling of the inter-
and so on. Furthermore, novel reactions via electrochemically- mediate (2) with the produced methoxy radicals, and 4 as a
generated intermediates can be expected. result of the self coupling of 2 (Scheme 1). Recently, anodic
It is known that hydroxyl radicals can be generated at BDD methoxylation of 2-oxozolidinone using BDD electrodes has
electrodes by an anodic process at potentials below the oxy- also been reported.51
gen evolution potential in an aqueous solution.32­37 Generally, 4.2 Anodic Coupling Reactions. The formation of the
hydroxyl radicals are adsorbed on the surface of the electrode biaryl skeleton is one of the most important subjects in organic
by direct electrochemical oxidation of water, and act as media- synthesis. Waldvogel et al. reported several examples show-
tors for oxygen evolution ((3) and (4)). ing C-H activation reactions and C-C coupling reactions of
H2 O ! HO• þ Hþ þ e ð3Þ phenols, arenes, and heterocyclic compounds using BDD elec-
þ 
trodes. In 2006, they reported the chemoselective anodic ortho-
2 HO• ! O2 þ 2H þ 2e ð4Þ coupling reaction of 2,4-dimethylphenol. Anodic oxidation
On the other hand, in the case of a BDD electrode, which is a with BDD electrodes under solvent-free conditions produced
“non-active electrode”,34 the interaction between the hydroxyl 2, 2¤-biphenol with very high selectivity. Other possible bi-

Bull. Chem. Soc. Jpn. 2018, 91, 1752–1762 | doi:10.1246/bcsj.20180268 © 2018 The Chemical Society of Japan | 1755
 1

“HFIP solvate cage”

Figure 5. ESR spectra obtained for the methoxy radical on

several electrode materials. Standard conditions: 10 mM B
solution of 5,5¤-dimethyl-1-pyrroline N-oxide (DMPO) in
0.1 M LiClO4/MeOH, Pt-wire cathode (Applied potential:
2
1.06 V vs. SCE), AN (hyperfine coupling constant of N)
value: 13.37 G (cf. 13.58 G), AH (hyperfine coupling 1
constant of H) value: 7.98 G (cf. 7.61 G). (Reproduced with
permission from ref. 50). Figure 6. Postulated electrocatalytic cycle of the anodic
conversion of isoeugenol (1). (Reproduced with permis-
sion from ref. 59).

(1) (3) 4 et al. proposed that the products of CO2 reduction depend on the
5
(2)
surface properties of the electrode material, i.e., the adsorption
of CO2 onto the electrode surface.62 “Active electrodes” which
Scheme 1. (Reproduced with permission from ref. 50). adsorb CO2 generate CO in aqueous solutions and HCOO¹ in
non-aqueous solutions. On the other hand, “non-active elec-
BDD trodes” which do not adsorb CO2, produce HCOO•¹ and CO2•¹,
respectively, in non-aqueous and aqueous solutions.
Note that CO2 reduction generally occurs at around the same
Scheme 2. potential as H2 evolution, which is a competitive reaction.62­65
Cyclic voltammetry of methanol containing tetrabutylammo-
products were observed in trace amounts.52 Then, they succeed- nium perchlorate (TBAP) at BDD electrodes in the absence
ed in improving the yield and selectivity of the homo-coupling of CO2 showed hydrogen evolution at a potential of around
of several phenols in the presence of highly fluorinated alco- ¹1.8 V (vs. Ag/AgCl). Accordingly, electrochemical reduction
hols, e.g., 1,1,1,3,3,3-hexafluoroisopropyl alcohol (HFIP).53 of CO2 was performed at a potential of ¹1.5 V in order to avoid
After these reports, they also developed anodic and selective hydrogen evolution. The main products with a BDD electrode
phenol-arene cross-coupling reactions in HFIP using a BDD were formaldehyde and formic acid, while hydrogen evolu-
electrode (Scheme 2).9,54­58 tion was suppressed due to the wide potential window of the
We also have reported electrochemical oxidation of BDD electrode.61 On the other hand, hydrogen was the main
isoeugenol in HFIP solution using BDD electrodes. A stereo- product with W and Cu electrodes, although acetic acid was
selective and electrocatalytic coupling reaction of isoeugenol also formed with a Cu electrode. As BDD with its sp3 carbon
(1) was observed. The particular C-C bond formation and bonds is an ideal “non-active electrode” known to have low
diastereoselectivity was induced by an interaction between the adsorption properties, CO2•¹ was possibly formed, followed
generated radical species (A) and another isoeugenol molecule. by the formation of formaldehyde or formic acid.66 This result
It is suggested that the generated radical species (A) confined was also different from that with a Sn electrode. In the case of
in the HFIP solvation cage induced the specific molecular glassy carbon electrodes, various products were generated, i.e.,
orientation. The reason for the stereoselective conversion is formaldehyde, formic acid, acetic acid, carbon monoxide, and
considered to be the solvate interaction between HFIP and the methane, besides hydrogen. This was probably due to the sp2
substrate (Figure 6).59 content of the glassy carbon, for which the adsorption prop-
4.3 Transformation by Cathodic Reduction. erties for CO2•¹ are different from those of BDD electrodes.
4.3.1 CO2 Reduction: The conversion of carbon dioxide Koper et al. elaborated on the mechanism of the CO2 reduction
(CO2) into useful chemicals has attracted much attention in reaction on BDD electrodes. They discussed the importance
recent years.60 Many kinds of electrodes, generally metals, have of disproportionation and other chemical reactions, including
been studied for the electrochemical reduction of CO2.61­65 Hori base-catalyzed Cannizzaro reactions.67

1756 | Bull. Chem. Soc. Jpn. 2018, 91, 1752–1762 | doi:10.1246/bcsj.20180268 © 2018 The Chemical Society of Japan
 Scheme 3. (Reproduced with permission from ref. 75).

Figure 7. Diagram of the two-compartment flow cell.

(Reproduced with permission from ref. 68).
Scheme 4. (Reproduced with permission from ref. 75).
(A)

and amine solutions have been used in CCS technology to

absorb CO2. For example, ammonia solution is a strong
absorber and has a high load capacity for CO2.69 Controlling
the reduced products from CO2 is also an important topic.
Consequently, CO2 reduction in aqueous ammonia solution on
BDD electrodes was performed. As a result, the main prod-
uct from CO2 reduction was methanol. The results show the
possibility of the practical application of reducing industrially
stored-CO2 in amine solutions.70
Furthermore, copper-modified BDD electrodes produced
(B) C2/C3 species such as ethanol, acetaldehyde, and acetone at
potentials as low as ¹1.0 V vs. Ag/AgCl.71 There are possi-
bilities that metal-modified BDD electrodes can be used not
only to produce valuable compounds but also to produce prod-
ucts at low potential. Recently, photoelectrochemical CO2
reduction using silver-modified BDD electrodes was also stud-
ied.72 Furthermore, selective production of ethanol and acetate
were achieved using a nanodiamond electrode co-doped with
boron and nitrogen and a nitrogen-doped nanodiamond elec-
trode, respectively.73,74
4.3.2 Cathodic Reductive Coupling: Electrochemical
reductive coupling reactions using BDD electrodes have been
reported.75 The radical intermediate derived from one-electron
Figure 8. (A) Faradaic efficiency and (B) concentration of reduction of phenylacrylate (Scheme 3) is different from the
HCOOH by the electrochemical reduction of CO2 with one obtained by anodic oxidation of 4-hydroxyphenyl-1-
a BDD electrode at 2 mAcm¹2 and a flow rate of 200 propene (Scheme 4). Novel neolignan-type dimeric compounds
mLmin¹1. (Reproduced with permission from ref. 68). can be expected from the reductive dimerization of cinnamic
acid derivatives.
In order to improve CO2 reduction on BDD electrodes the Electrochemical reduction of ester methyl cinnamate (6) at a
electrochemical conditions, especially on alkali-metal cations constant current in acetonitrile produced (7), (9), and the hy-
in the solution, were optimized. Furthermore, stable and highly drodimer, dimethyl 3,4-diphenylhexanedioate (8) (Scheme 5).
efficient production of formic acid was achieved by using a Although glassy carbon electrodes gave similar products to
flow cell system (Figure 7). Not only was the faradaic effi- those of BDD electrodes, Pt and Mg electrodes showed mainly
ciency for the production of formic acid high (94.7%), but also hydrogen evolution. The hydrodimer (8) was then successfully
the rate of production was increased to 473 ¯molm¹2s¹1, due to converted by chemical reactions to neoligan-type compounds.75
the effective mass transport of CO2 to the electrode surface Electrochemical syntheses using BDD electrodes have some
(Figure 8).68 advantages in comparison with syntheses using conventional
Carbon dioxide capture and storage (CCS) technology for electrodes. This is due to the unique electrochemical properties
reducing CO2 emissions has also been thoroughly developed, of BDD electrodes, which are its inert sp3 carbon surface, its

Bull. Chem. Soc. Jpn. 2018, 91, 1752–1762 | doi:10.1246/bcsj.20180268 © 2018 The Chemical Society of Japan | 1757
 Table 1. Boron concentration and resistivity of the synthetic
+ films. (Reproduced with permission from ref. 81)
(7) B/C ratio of boron density film resistivity
sample feed gas by SIMS thickness at RT
(ppm) (atom cm¹3) (μm) (³cm)
(6) BDD-A 100 7.1 © 1019 12 1.7
(R = CH4) BDD-B 100 5.9 © 1019 16 0.90
(8) BDD-C 10,000 2.6 © 1021 1.6 1.8 © 10¹3
BDD-D 50,000 5.5 © 1021 3.2 3.3 © 10¹3

(a)

(9)

Scheme 5. (Reproduced with permission from ref. 75).

wide potential window and that active species such as radicals

can be generated. Therefore, the applications of BDD elec-
trodes for electrochemical synthesis are very promising for
novel chemical transformations.

5. Fundamental Studies
(b)
Although BDD is a superior electrode material for various
electrochemical applications, the properties required depend on
each application. Therefore, the electrode design appropriate
for each application is very important in order to bring out
the full potential of the electrode. Although the inert (i.e. “inac-
tive”) properties of BDD electrodes are thought to be advanta-
geous, “active” BDD electrodes can also be used as versatile
electrodes if it is possible to control the properties. It is known
that the electrochemical properties of BDD electrodes can be
affected by the doping concentration,76,77 the surface termi-
nation77,78 and the sp2-bonded carbon impurities.79,80 It is,
therefore, expected that new electrochemical properties can be Figure 9. Background current­voltage curves of synthetic
found that make use of, for example, the sp2 and sp3 bonded BDD electrodes in 0.1 mol dm¹3 HClO4 solutions, (a)
carbon in highly boron-doped diamond (h-BDD) containing before and (b) after anodic treatment at a scan rate of
non-diamond carbon impurities. 0.1 Vs¹1. (Reproduced with permission from ref. 81).
However, the origin of the characteristics of both sp2 and
sp -bonded carbon in disordered h-BDD materials is still
3
doped diamond films (lower than 1020 atoms cm¹3) and one
unclear. On the other hand, recent progress in transmission with heavily boron-doped diamond films (higher than 1021
electron microscopy (TEM) techniques has enabled the local atoms cm¹3). BDD films containing sp2-bonded carbon impu-
structure of boron in a diamond matrix and that at dislocations rities were prepared for each boron doping level. These four
in h-BDD to be investigated by atomic resolution imaging and different types of BDD, in boron doping level and sp2-bonded
spectroscopy. carbon content, were fabricated (BDD-A, B, C, and D:
Thus, firstly, we studied the effect of sp2-bonded carbon Table 1), and their electrochemical properties and electrochem-
impurities on the electrochemical properties of electrodes with ical applications were investigated.
different boron doping levels. Four different BDD electrodes Figure 9 shows a CV in 0.1 M HClO4 for the BDD
with different boron doping levels and sp2-bonded carbon con- electrodes (a) before and (b) after anodic treatment. The most
tent were prepared and their electrochemical properties and interesting feature in Figure 9 is the voltammogram of BDD-D.
their application were discussed.81 Then, secondly, we used This changed drastically after the anodic treatment. The poten-
TEM and electron energy-loss spectroscopy (EELS) to clarify tial window was reduced to almost half that of one with hydro-
the relationship between the local structure and the electro- gen termination, and the background current increased by more
chemical properties of h-BDD. In particular, we focused on the than a hundredfold. The voltammogram of BDD-D looks like
local structure around the boron atoms and the non-diamond that of a glassy carbon (GC) electrode rather than an ordinary
carbon sites in strongly disordered samples with sp2-bonded BDD electrode. The difference between BDD-D and BDD-C
carbon impurities.82 suggests that the sp2-bonded carbon impurities significantly
5.1 Tailored Synthesis. Two groups with different boron contribute to the electrochemical properties. On the other hand,
doping levels were prepared, a group with moderately boron- for moderately boron-doped diamond, there is no notable

1758 | Bull. Chem. Soc. Jpn. 2018, 91, 1752–1762 | doi:10.1246/bcsj.20180268 © 2018 The Chemical Society of Japan
 (a)

(b)

Figure 11. Rough map of the appropriate BDD electrode

depending on the application.

produced a much higher concentration of ozone with high

current efficiency.
For the generation of ozone, oxygen radicals and oxygen
formed through further oxidation of the hydroxyl radicals are
the reactants. The sp2-bonded carbon impurities in BDD-D
Figure 10. The variation with potential of (a) the FIA might play a role not only as active sites but also as stronger
current signal with 1 mmol dm¹3 formic acid injection and adsorption sites. These can give longer adsorption times and
(b) the background current for the synthetic BDD electro- longer adsorption times for oxygen can promote the formation
des and a glassy carbon electrode. At more positive poten- of ozone. That is, BDD-D has an advantage for ozone genera-
tials than displayed, measurements were disturbed by tion compared to BDD-A, B, and C.
bubble formation. In (a), the background currents were Based on this work, we proposed a rough map of the appro-
subtracted from the observed current. (Reproduced with priate BDD electrode for each application (Figure 11).
permission from ref. 81). 5.2 TEM/EELS Study. As mentioned above, the role
of sp2 carbon impurities in BDD is very important. However,
difference between the presence and absence of sp2-bonded the electrochemical properties originating from sp2 and sp3-
carbon impurities. bonded carbon in disordered h-BDD materials are still unclear.
Also, the suitability of using these electrodes for wastewater Therefore, in order to clarify the relationship between the local
treatment with hydroxyl radicals was estimated by the oxida- structure and the electrochemical properties of h-BDD, TEM
tion of formic acid. Formic acid is used as a model compound and electron energy-loss spectroscopy (EELS) of h-BDD were
for evaluating the capability for degrading organics because of performed. The local structure around the boron atoms and the
the simple oxidation reaction, which is: non-diamond carbon sites in strongly disordered samples with
sp2-bonded carbon impurities was discussed.
HCOOH þ 2 •OH ! 2H2 O þ CO2
Here, two distinct h-BDD samples with respect to the
Figure 10 shows the variation of (a) the signal current and amount of non-diamond sp2-bonded carbon impurities were
(b) the background current with potential. The trends for BDD- prepared (1 at. %, and 3 at.%). Cyclic voltammograms with a
D and GC are similar. This is because the oxygen evolution 1 at. % h-BDD electrode in 0.1 M HClO4 aqueous solution after
reaction mechanisms for BDD-D and GC are similar. It is anodic treatment showed a wide potential window with low
suggested that the surface functionalities of BDD-D, which capacitive current, which is one of the typical characteristics of
can react with hydroxyl radicals, catalyze the oxygen evolu- diamond electrodes.8 In contrast, with the 3 at.% h-BDD elec-
tion reaction, and the reactions between formic acid and the trode, there was a radical increase in background current after
hydroxyl radicals hardly occurs with BDD-D. the anodic treatment (Figure 12). These results were consistent
Then, we also examined electrochemical ozone generation with the ones shown in Figure 9.
(data not shown). The results showed that BDD-A and BDD-B Figure 13 shows cross-sectional TEM images of the 1 at.%
had similar properties for ozone production. All the measure- and 3 at.% h-BDD films, both of which indicate micrometer-
ments suggested that the presence of sp2-bonded carbon impu- sized columnar growth. The 1 at.% h-BDD film is densely
rities in moderately boron-doped diamond had little influence packed with crystallites, while the 3 at.% h-BDD film contains
on the electrochemical properties. Heavily boron-doped dia- some voids at the grain boundaries, as shown in Figures 13a
mond (BDD-C and BDD-D) exhibited high efficiencies for and 13b.
ozone production compared to moderately boron-doped dia- Figure 13c shows EELS acquired from the grain interiors in
mond (BDD-A and BDD-B). Note that BDD-D in particular both samples. The well-defined K edge of carbon is shown

Bull. Chem. Soc. Jpn. 2018, 91, 1752–1762 | doi:10.1246/bcsj.20180268 © 2018 The Chemical Society of Japan | 1759
 Intensity (a.u.)
270 275 280 285 290 295 300 305 310
Energy / eV

Figure 14. (a) Cross-sectional TEM image of 3 at.% h-

BDD. (b) B-K edge in EELS mapping of the green
Figure 12. Cyclic voltammograms in 0.1 M HClO4 before rectangular region in (a), and (c) 1s¼π* peak of the C-K
and after anodic oxidation with a scan rate of 100 mV/s. edge in EELS mapping of the green rectangular region in
(Reproduced with permission from ref. 82). (a). (d) Magnified TEM image of the red rectangular region
in (a) and a selected-area diffraction pattern from the grain
boundary (GB) phase. (e) EEL spectra from the grain
interior, the grain boundary and graphite as a reference.
(Reproduced with permission from ref. 82).

homogeneous solid solutions in both samples. Furthermore, the

typical C-K edge of sp3-bonded diamond (1s ¼ σ*) between
290 and 310 eV is observed in both samples, while the pre-peak
at 283 eV (1s ¼ π*) is clearly observed in the 3 at.% h-BDD.
This suggests that the 3 at.% h-BDD contains many more sp2-
bonded carbon impurities in the grains than the 1 at.% h-BDD.
Figure 14a shows another TEM image of the 3 at.% h-BDD.
The corresponding filtered EELS images with the B-K edge
(Figure 14b) and the C-K edge (Figure 14c) clearly show that a
(c) boron deficient phase has formed along the grain boundaries.
The EEL spectrum from the grain boundary phase, shown in
Figure 14d, is clearly characteristic of sp2-bonded graphite, as
shown in Figure 14e.
Based on the analysis, the formation of the graphite phase
and its contribution to the electrochemical properties are dis-
cussed. The high durability of 3 at.% h-BDD originates from
the main sp3-diamond phase. The graphite phase is formed
mainly at the grain boundaries and is responsible for the glassy
carbon-like electrochemical properties. The drastic increase in
background current after the anodic treatment is possibly due
to electrochemical activation of this graphite phase and/or
enlargement of the surface area by electrochemical oxidation
of sp2-bonded carbon to CO2. Regarding the electrochemical
Figure 13. Cross-sectional TEM images of (a) 1 at.% h-
applications, these two types of h-BDD showed totally differ-
BDD, (b) 3 at.% h-BDD and (c) their EEL spectra acquired
ent suitability for wastewater treatment and ozone generation
from the grain interiors. The arrows indicate voids. (Repro-
duced with permission from ref. 82). applications.81 An h-BDD electrode containing sp2-bonded
carbon impurities is not appropriate for wastewater treatment
but is highly suitable for ozone generation.
from 284 eV and above. The boron concentration estimated Although it is not easy to understand the properties in detail,
from integrating the edge intensities (0.9 « 0.2 at.% and not only should geometric changes be taken into account, but
3.0 « 0.4 at.% for 1 at.% and 3 at.% h-BDD, respectively) are also the surface chemistry needs to be considered. It is sug-
consistent with the estimates from Glow Discharge Optical gested that the surface structure of the grains would turn into
Emission Spectrometry (GD-OES) (data not shown). Boron more stable structures, i.e., sp2-hybridized carbons, to relieve
atoms are almost uniformly distributed over the grains to be the internal stress of the grains. That is, the formation of the

1760 | Bull. Chem. Soc. Jpn. 2018, 91, 1752–1762 | doi:10.1246/bcsj.20180268 © 2018 The Chemical Society of Japan
 Sensor for environmentally Waste water treatment 6 K. Arihara, C. Terashima, A. Fujishima, J. Electrochem.
important species
Soc. 2007, 154, E71.
Heavy metals, Chlorine, etc Improvement 7 A. Kapałka, B. Lanova, H. Baltruschat, G. Fóti, Ch.
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Environmental 8 Y. Einaga, J. Appl. Electrochem. 2010, 40, 1807.
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Neurotransmitter
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Biomedical
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Glucose, Uric acid, Oxalic acid, Electrochemical organic 12 Diamond Electrochemistry, ed. by A. Fujishima, Y. Einaga,
Protein etc synthesis
T. N. Rao, D. A. Tryk, Elsevier and BKC, 2005.
Figure 15. Electrochemical applications of diamond 13 A. Kraft, Int. J. Electrochem. Sci. 2007, 2, 355.
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Characterization, and Applications, ed. by E. Brillas, C. A.
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6. Conclusion 17 T. Watanabe, K. Akai, Y. Einaga, Electrochem. Commun.
In this article, recent developments in BDD electrodes for 2016, 70, 18.
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21 J. M. Halpern, S. Xie, G. P. Sutton, B. T. Higashikubo,
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especially Dr. K. Natsui, Dr. T. Yamamoto, Prof. S. Nishiyama Doi, M. Takai, I. Findlay, H. Kusuhara, Y. Einaga, H. Hibino,
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