Accepted Manuscript

Two-dimensional boron-doped graphyne nanosheet: A new metal-free catalyst for

oxygen evolution reaction

Xiangkai Kong, Yimin Huang, Qiangchun Liu

PII: S0008-6223(17)30789-3
DOI: 10.1016/j.carbon.2017.08.003
Reference: CARBON 12265

To appear in: Carbon

Received Date: 11 June 2017

Revised Date: 2 August 2017
Accepted Date: 3 August 2017

Please cite this article as: X. Kong, Y. Huang, Q. Liu, Two-dimensional boron-doped graphyne
nanosheet: A new metal-free catalyst for oxygen evolution reaction, Carbon (2017), doi: 10.1016/
j.carbon.2017.08.003.

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Two-dimensional boron-doped graphyne nanosheet: a new

metal-free catalyst for oxygen evolution reaction

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Xiangkai Konga,b,*, Yimin Huangc, Qiangchun Liua,*

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a
School of physics and electronic information, Huaibei Normal University, Huaibei 235000, Anhui, P. R. China.
E-mail: kxk@chnu.edu.cn, qchliu@chnu.edu.cn
b
Department of Material Science and Engineering, University of Science and Technology of China, Hefei 230026,

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Anhui, P. R. China.
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c
Department of Chemistry, Purdue University, West Lafayette 47907, IN, USA.
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Abstract
Highly efficient, economical and environmentally friendly materials are important and
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remain a challenge in the renewable energy conversion and storage technologies. The
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oxygen evolution reaction has been envisaged on a two-dimensional graphyne (GY)

nanosheet based on density functional theory framework. Local electronic/chemical
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environment on GY surface is significantly influenced and can be controlled by

doping foreign atoms with different formats, which will contribute to its improved
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catalytic performance. Henceforth, free energy change diagrams, Raman spectra,

natural bond orbital charge density, charge density difference, and other data have
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been calculated and discussed. It is suggested that boron doping at edge sites on GY is
the ideal candidate for high OER activity, which is efficient as carbon-based
electrocatalysts for water splitting and metal-air batteries.
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1. Introduction
Clean and sustainable energy technologies, such as direct solar driven water-splitting
and rechargeable metal-air batteries, are promising in various renewable energy
conversion and storage system. Oxygen evolution reaction (OER) is the key enabling
process for these future energy sources. Generally, it experiences a complex

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four-electron oxidation process and requires a high overpotential to proceed due to the
sluggish kinetics. It is considered as the critical bottleneck for rate determining step

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and efficient OER electrocatalysts must be used to drive high current density at low
overpotential.[1,2] To date, the most frequently used benchmarking OER catalysts are

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noble metal oxides. However, the high cost and scarcity of such catalysts constrain
their widespread uses.[3] As a result, the design and exploration of highly efficient,

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economical and environmentally friendly OER catalysts are attractive and essential.
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Two-dimensional (2D) nanostructures and carbon materials, such as doped
graphene, have been widely investigated as artificial OER catalysts.[4-6] As new 2D
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carbon allotropes, graphyne (GY) and graphdiyne (GDY) are composed of one atom
thick layer of carbon sheet, with highly π-conjugated structure. Different from
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graphene, they are constructed by the mixture of sp and sp2 hybridized carbon atoms.
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In addition, the disparity between them is the number of connecting sp carbon atoms
between two nearby hexagonal rings, where there are two and four sp hybridized
carbon atoms for GY and GDY, respectively.[7] Recently, Li and his co-workers have
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fabricated large area GDY films on the surface of copper via a cross-coupling reaction
using hexaethynylbenzene, and Wu et al. have introduced GDY as the hole transfer
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layer into a photoelectrochemcial water splitting cell.[8,9] In addition, its mechanical

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properties and molecular electronics have been intensively studied.[10,11] For GY, the
electron, phonon, and thermoelectric transport properties have been studied and
demonstrated compared and contrasted with those of graphene.[12] Meanwhile, we
have carried out density functional theory (DFT) investigations and concluded it
could be a good candidate for surface enhanced Raman scattering and oxygen
reduction reaction in fuel cells.[13] However, it still remains an open question whether
GY has the potential to be used in the water oxidation.
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In this study, we investigate the OER activity of GY responding to the

functionalized doping engineering. Nitrogen and boron are selected as the doping
elements because they are adjacent to carbon in the Periodic Table, effective to control
the properties of carbon materials, and can be easily obtained by treatment with
nitrogen and boron containing compounds in experiments. It is concluded that the

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types of foreign atoms and the doping sites are the determining factors for its catalytic
ability. Co-doped systems seem no significant contributions. To address these issues,

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free energy change diagram calculations, Raman spectra simulations, natural bond
orbital (NBO) analysis, and charge density difference (CDD) discussions have been

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carried out sequentially.

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2. Method of Calculations
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In this theoretical study, all the calculations are carried out using the DFT scheme, as
implemented in the Gaussian 09 package.[14] All ground-state geometries are
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optimized by the B3LYP functional and there are no imaginary frequencies, ensuring
that all of the structures are stable. The 6-31G* basis set is employed in all the below
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calculations, supplying polarization functions to C, H, N and O atoms. Both the

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functional and basis set are selected based on the previous work and considering the
large systems here.[5,13] Geometry optimizations are carried out until the gradient
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forces are smaller than a threshold value of 0.012 eV and the simulations are all
performed with a (75, 302) pruned grid. The charge distribution analysis is completed
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using the Natural Bond Orbital (NBO) method.

The following four electron reaction paths are adopted to identify fundamental aspects
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of the water oxidation process, which is also depicted in Figure 2a:

OH- + * → *OH + e-
*OH + OH- → *O + H2O + e-
*O + OH- → *OOH + e-
*OOH + OH- → *O2 + H2O + e-
*O2 → O2 + *
where * represents an active site on the GY surface, and the symbols “*O2”, “*OH”,
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“*O” and “*OOH” stand for the related intermediates residing on the electrocatalysts.
The rate limiting step can be either transforming from *OH to *O or the formation of
*OOH from *O as evidenced by the above set of equations. In order to find out the
potential-determining step, the reaction free energies are calculated as follows:
∆G*O = E(*O) - E(*) - EH2O + EH2 + ∆ZPE - T∆S

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∆G*OH = E(*OH) - E(*) - EH2O + 1/2EH2 + ∆ZPE - T∆S
∆G*OOH = E(*OOH) - E(*) - 2EH2O + 3/2EH2 + ∆ZPE - T∆S

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In which, ∆G*O, ∆G*OH, ∆G*OOH and E(*O), E(*OH), E(*OOH) are the free
energies and the ground state energies of GY substrate adsorbed with *O, *OH and

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*OOH, respectively. E(*) is the optimized DFT energy of a clean electrocatalyst, and
in addition, EH2O and EH2 are the calculated energies of free H2O and H2 molecules.

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Apart from these, zero point energy (ZPE) and entropy corrections have been
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considered, with ∆ZPE, ∆S and T standing for the ZPE change, entropy change and
the temperature. The ZPE values can be obtained directly form the optimized files and
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the TS corrections for H2 and H2O are 0.40 and 0.67 eV, respectively.[15,16]
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3. Results and Discussions

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The model of GY discussed here is selected from Zhou’s structure, which

contains 66 carbon atoms and is terminated with 18 hydrogen atoms at the
edges.[17] Detailed calculated method can be referred in the supplementary
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material. As shown in Figure S1, the optimized pristine GY exhibits a planar

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sheet-like configuration with large holes structure surrounded by sp-hybridized

carbon atoms, which is beneficial for mass transportation and diffusion,
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contributing to the water oxidation efficiency. The OER activity is significantly

determined by the interaction between the catalyst surface and the generated
oxygen intermediates, thus the reaction free energies of the adsorbed *OH, *O
and *OOH species have been calculated as previous reports, which are pivotal
descriptors for estimating the catalytic oxygen evolution ability.[15,16,18] Figure
1a provides the calculated free energy variation diagrams for pristine GY, in
which *OOH formation with 2.42 eV is the largest free energy change step, far
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from the theoretical value of 1.23 eV. Simultaneously, the *OH adsorption step
also displays a large free energy variation of 2.10 eV, which indicates a much
high potential is needed to accelerate the oxygen evolution process over pristine
GY catalyst.

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Figure 1. The free energy diagrams for the OER at zero potential over (a)
pristine GY, (b) N5-1-GY, (c) N3-1-GY, (d) N2-1-GY, (e) B5-GY, (f) B3-GY,
(g) B2-GY, and (h) B1-GY.
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To improve the electrocatalytic performance, increasing the reactivity and

number of active sites are two effective routes, as active sites play a crucial role in the
catalytic process. Defect engineering is anticipated to achieve this enhanced
performance, which can be carried out via doping foreign atoms in the GY substrate.
Nitrogen and boron are the adjacent atoms to carbon, which are normally used to

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strengthen the special performance of carbon materials.[19] Therefore, pristine GY is
functionalized with nitrogen and boron impurity substitution, constituting a doping

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percentage of 1.5%. We first develop a series of models for GY with single atom
dopant at different sites, as shown in Figure S1. All the oxygen intermediates (*OH,

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*O, and *OOH) tend to interact with positively charged sections on the doped GY
catalysts owing to the electrostatic attraction at the interface. Nitrogen will induce

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local high positive charge density around itself because of its higher electronegativity
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than carbon. Thus, for each N-doped structure, we consider the two nearest carbon
atoms next to the doped nitrogen as the OER occurring sites, which is the same case
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as in nitrogen-doped graphene.[20,21-23] Conversely, boron is in the opposite case,

which can be directly regarded as the reaction site for intermediates combination, due
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to its lower electronegativity than carbon.

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We have presented here the band gaps of these nitrogen- and boron-doped GY in
Figure S2, which are obtained from the difference between the highest occupied
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molecular orbital and the lowest unoccupied molecular orbital. Obviously, either
nitrogen or boron doped structure can exhibit a significantly lower band gap
compared with the pristine case, demonstrating the improving conductivity on GY,
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which can accelerate the charge transfer efficiency and enhance the OER activity.
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Furthermore, nitrogen and boron will reduce the band gaps for α and β electrons,
respectively, and this can be explained by the different induced doping mechanisms,
where nitrogen will donate electrons and boron tends to withdraw electrons from the
GY substrate.
Figure 1 demonstrates that all of these GY catalysts with different doping sites
exhibit an uphill OER character toward the whole oxygen evolving procedure. For
nitrogen-doped cases, N2-1-GY exhibits the lowest required potential of 1.80 eV
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among the three to complete the whole water oxidation procedure (the naming
approach can be found in Figure S3). Meanwhile, transformation from *O to *OOH
remains as the rate-determining step for these nitrogen-doped structures, indicating
similar OER processes occurring over the nitrogen-doped electrocatalysts. To further
reduce the free energy variation, we have presented the investigations on boron-doped

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configurations. It is clear that boron functionalizing can provide higher activity for
GY-based catalysts toward oxygen evolution, and among which, B1-GY demonstrates

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the lowest limiting energy of 1.57 eV, corresponding to an overpotential of 350 mV.
The resultant unique structure imparts reduced barrier for oxygen containing

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intermediates adsorption and conversion, ensuring high activity in catalyzing oxygen
evolution, which is comparable to metal catalysts (300-400 mV overpotential required

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for LaNiO3 and SrNiO3) and even better than some doped graphene (more than 400
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mV overpotential needed for graphitic, pyridine or pyrrolic N-doped graphene).[5,20]
Meanwhile, other boron-doped GY also exhibit reduced overpotential than nitrogen
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counterparts, suggesting the advantages of boron doping in this GY system. In

addition, the least overpotential required for OER processing over B1-GY illustrates
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the edge effects, suggesting more active OER catalysts can be constructed by boron
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doping at the edge-sites of GY. Notably, these boron-doped structures exhibit

different rate-determining steps. The rate-determining steps are ascribed to the
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involved conversion processes, reflecting the different influences caused by changing

doping sites.
Before oxygen molecules formed and releasing, the whole reaction process
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involves three conversion steps, from the adsorbed *OH to *O and then transforming
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into *OOH, as depicted in the optimized structures in Figure 2a. Obviously, there are
distinct distortions occurring on the doped area in the vertical direction, owing to the
strong interactions between the intermediates and GY surface. While the parts far
from this doped atom almost remain the planar structure as before (Figure S1b).
Figure 2b shows the Sabatier-type volcano plots for different doped GY. It is widely
accepted that Sabatier principle is an efficient qualitative concept in chemical analysis,
and the energy difference between *O and *OH adsorption is an advantageous
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descriptor to demonstrate the OER performance, because it correlates with two

intermediates adsorption rather than only one.[24] B1-GY exhibits the lowest
overpotential with the descriptor ∆G(*O)- ∆G(*OH) of 1.36 eV, which is the closest
to the volcano peak among all the discussed GY-based electrocatalysts. Moreover,
phosphorus has also been considered as the functionalized atom as it has lower

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electronegativity than carbon, in the same instance with boron. However, their
activities are insufficient with the descriptor values of almost 0 for their *O and *OH

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adsorption energy difference, much far from the peak position. Besides, bi-doping
cases such as boron and nitrogen co-doped GY system has also been taken into

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consideration. However, their high overpotentials as well as low adsorption energy
difference descriptors make them deficient for evolving oxygen via water splitting.

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Figure 2. (a) The OER steps on B1-GY, with the gray, white, red and pink balls
standing for carbon, hydrogen, oxygen and boron atoms, respectively, (b) volcano
plot of the overpotential against the universal descriptor ∆G(*O)- ∆G(*OH) over
different catalysts, and (c) linear relation of the free energies of *OOH versus *OH on
GY-based catalysts.
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The relationship between the adsorption free energies of *OOH and *OH over
these GY-based catalysts are documented in Figure 2c. The linear fitting is easily
obtained, which demonstrates the y=0.92x+3.05 relation with a constant of 3.0 eV,
which is close to those reported on functionalized graphene materials.[6,20,24] Different

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deviations are observed on these doped metal free configurations, and this can be
explained by the change of electronic structures on GY surface induced by doping

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types and sites, indicating the artificial manipulation of the intermediates adsorption
on GY.

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Further, to understand the enhanced catalytic mechanism, Raman spectroscopic
study has been carried out based on DFT calculations. As a control, pristine GY

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Raman spectrum displays two peaks at 1378.4 and 1542.3 cm-1 (Figure 3a), which are
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attributed to the breathing vibration, and the first-order scattering of the E2g mode for
stretching vibration of sp2 carbon domains in aromatic rings, denoted as D band and G
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band, respectively. This is in line with the GDY Raman spectrum characterized in
experiment.[8] Doping with foreign atoms will change the Raman spectrum and have
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an influence on its peak positions (Figure 3b). Meanwhile, it is found the peak shift
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caused by boron doping is larger than that of the nitrogen doped case. The intensity
ratio (ID/IG) is a good response to the quality of GY nanosheet. As shown in Figure
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3c, the intensity ratio of B1-GY is 1.97, significantly higher than that of B3-GY and
B5-GY. Meanwhile, the bond length distortion of B1-GY is also the largest, in
accordance to the Raman ratio, and the variation trends of them match well. These
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discussions indicate the high defects and low order are obtained on 2D GY, caused by
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boron doping at the edge site.

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Figure 3. (a) Simulated Raman spectra and (b) peak positions of D band and G band,
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(c) Intensity ratio of ID/IG and the bond (between boron and its neighbor sp2 carbon
atom) distortion, and (d) NBO charge density of doped GY.
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Furthermore, we have calculated the charge density distribution based on the

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NBO method, because the electrostatic attraction at the interface should be the main
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driving force for the generated oxygen species adsorption. As shown in Figure 3d,
B1-GY exhibits the smallest positive charge density on its doped boron atoms, which
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can provide the most moderate interaction for the intermediates adsorption. A strong
attractive force will catch the intermediate too tightly, not conductive to its further
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transformation and conversion. At this juncture, the smallest local positive charge
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density will combine the *OH, *O, and *OOH species neither too strong nor too
loosely, facilitating the reaction processing continuously.
CDD can give the precise information to illustrate the interaction at the interface.
The free energy change results in Figure 2 have indicated the *O to *OOH conversion
is the rate-determining step for both pristine and B1-GY catalysts. Henceforth, we
have carried out the CDD calculation for *O and *OOH species on these two models,
respectively, as displayed in Figure 4. When the single oxygen atom is generated and
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adsorbed on the GY surface, charge redistribution occurs in the GY plane as marked

by the arrow in Figure 4a, where some electrons transfer from the GY substrate to the
adsorbed *O. In contrast, there is no obvious redistribution in the B1-GY plane, just
with a little electron transferring around the boron surface. For *OOH adsorption,
there is almost no electron redistribution occuring in the carbon section of pristine GY,

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while the charge transfer density is more significant for B1-GY model, where the
charge redistribution areas reach the doped boron atom significantly. These results

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imply that compared to the pristine GY, B1-GY can adsorb the *O more loosely and
catch the *OOH more tightly, which can also be easily confirmed with the adsorption

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energy listed in Table S1. This will facilitate the conversion from *O to *OOH and
improve its electrocatalytic performance, as a too high *O binding will prevent its

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transformation to following species.
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Figure 4. The calculated CDD image at the interface for *O on (a) pristine GY and
(b) B1-GY, and *OOH adsorbed on (c) pristine and (d) B1-GY, respectively. The
isovalue is 0.02 a.u.. The purple and cyan stand for electron and hole, respectively.
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4. Conclusions

In summary, we have constructed a set of doped GY models, and OER

performance over these electrocatalysts formed with different doping types and
sites are analyzed by DFT calculations. Free energy change diagrams, Raman
spectra, NBO charge density distribution, and CDD calculations are employed

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and performed to illustrate the controllable local chemical/electronic structure
modifications caused by doping formats. As a matter of fact, B1-GY exhibits

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the minimum overpotential and is identified as the optimal catalyst for OER
application. The moderate positive charge density and high structural defective

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distortion induced by edge boron doping on GY are a good design for high
OER activity. All the boron doping exhibit better performance than

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nitrogen-doped and its pristine counterparts. It is anticipated to have boron
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functionalized GY as catalysts for water-splitting device and metal-air battery
cells, from the perspective of highly efficient, economical and environmentally
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friendly materials.
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Acknowledgements
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This work is supported by the National Natural Science Foundation of China

(51602116), Anhui Natural Science Foundation (1708085QB40), China Postdoctoral
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Science Foundation (2016M600492) (to X. K.), and Anhui Natural Science

Foundation (1508085ME100), Natural Science Fund for Colleges and Universities in
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Anhui Province (KJ2017ZD31) (to Q. L.). The calculations have been completed on
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the Supercomputing system in the Supercomputing Center of USTC.

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