Parallelized Reaction Pathway and Stronger Internal
Band Bending by Partial Oxidation of Metal Sulfide–Graphene
Composites: Important Factors of Synergistic Oxygen Evolution Reaction
Enhancement
Version 2 2018-04-20, 17:18
Version 1 2018-04-10, 15:19
Posted on 2018-04-20 - 17:18
The electrocatalytic performance
of transition metal sulfide (TMS)–graphene composites has been
simply regarded as the results of high conductivity and the large
surface/volume ratio. However, unavoidable factors such as degree
of oxidation of TMSs have been hardly considered for the origin of
this catalytic activity of TMS–graphene composites. To accomplish
the reliable application of TMS-based electrocatalytic materials,
a clear understanding of the thermodynamic stability of TMS and effects
of oxidation on catalytic activity is necessary. In addition, the
mechanism of charge transfer at the TMS–graphene interface
must be studied in depth to properly design composite materials. Herein,
we report a comprehensive study of the physical chemistry at the junction
of a Co1–xNixS2–graphene composite, which is a prototype
designed to unravel the mechanisms of charge transfer between TMS
and graphene. Specifically, the thermodynamic stability and the effects
of oxidation of TMSs during the oxygen evolution reaction (OER) on
the reaction mechanism are systematically investigated using density
functional theory (DFT) calculations and experimental observations.
Cobalt atoms anchored on pyridinic N sites in the graphene support
form metal–semiconductor (SC) junctions, and the internal band
bending at these junctions facilitates electron transfer from TMSs
to graphene. The junction enables fast sinking of the excess electron
from OH– adsorbate. Partially oxidized amorphous
TMS layers formed during the OER can facilitate adsorption and desorption
of OH and H atoms, boosting the OER performance of TMS–graphene
nanocomposites. From the DFT calculations, the enhanced electrocatalytic
activity of TMS–graphene nanocomposites originates from two
important factors: (i) increased internal band bending and (ii) parallelized
OER pathways at the interface of pristine and oxidized TMSs.
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Han, HyukSu; Kim, Kang Min; Choi, Heechae; Ali, Ghulam; Chung, Kyung Yoon; Hong, Yu-Rim; et al. (2018). Parallelized Reaction Pathway and Stronger Internal
Band Bending by Partial Oxidation of Metal Sulfide–Graphene
Composites: Important Factors of Synergistic Oxygen Evolution Reaction
Enhancement. ACS Publications. Collection. https://doi.org/10.1021/acscatal.8b00017
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AUTHORS (13)
HH
HyukSu Han
KK
Kang Min Kim
HC
Heechae Choi
GA
Ghulam Ali
KC
Kyung Yoon Chung
YH
Yu-Rim Hong
JC
Junghyun Choi
JK
Jiseok Kwon
SL
Seung Woo Lee
JL
Jae Woong Lee
JR
Jeong Ho Ryu
TS
Taeseup Song
SM
Sungwook Mhin