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Title: Designing Boron Nitride Islands in Carbon Materials for Efficient Electrochemical Synthesis of Hydrogen Peroxide

Abstract

Heteroatom-doped carbons have drawn increasing research interest as catalysts for various electrochemical reactions due to their unique electronic and surface structures. In particular, co-doping of carbon with boron and nitrogen has been shown to provide significant catalytic activity for oxygen reduction reaction (ORR). However, limited experimental work has been done to systematically study these materials, and much remains to be understood about the nature of the active site(s), particularly with regards to the factors underlying the activity enhancements of these boron–carbon–nitrogen (BCN) materials. Herein, we prepare several BCN materials experimentally with a facile and controlled synthesis method, and systematically study their electrochemical performance. We demonstrate the existence of h-BN domains embedded in the graphitic structures of these materials using X-ray spectroscopy. These synthesized structures yield higher activity and selectivity toward the 2e ORR to H2O2 than structures with individual B or N doping. We further employ density functional theory calculations to understand the role of a variety of h-BN domains within the carbon lattice for the ORR and find that the interface between h-BN domains and graphene exhibits unique catalytic behavior that can preferentially drive the production of H2O2. Here, to the best of our knowledge, this is the firstmore » example of h-BN domains in carbon identified as a novel system for the electrochemical production of H2O2.« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1];  [2];  [2];  [1];  [1]; ORCiD logo [1];  [2];  [1];  [3]; ORCiD logo [3]; ORCiD logo [1]
  1. Stanford Univ., Stanford, CA (United States)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  3. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1459647
Grant/Contract Number:  
SC0008685; AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 140; Journal Issue: 25; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Chen, Shucheng, Chen, Zhihua, Siahrostami, Samira, Higgins, Drew, Nordlund, Dennis, Sokaras, Dimosthenis, Kim, Taeho Roy, Liu, Yunzhi, Yan, Xuzhou, Nilsson, Elisabeth, Sinclair, Robert, Norskov, Jens K., Jaramillo, Thomas F., and Bao, Zhenan. Designing Boron Nitride Islands in Carbon Materials for Efficient Electrochemical Synthesis of Hydrogen Peroxide. United States: N. p., 2018. Web. doi:10.1021/jacs.8b02798.
Chen, Shucheng, Chen, Zhihua, Siahrostami, Samira, Higgins, Drew, Nordlund, Dennis, Sokaras, Dimosthenis, Kim, Taeho Roy, Liu, Yunzhi, Yan, Xuzhou, Nilsson, Elisabeth, Sinclair, Robert, Norskov, Jens K., Jaramillo, Thomas F., & Bao, Zhenan. Designing Boron Nitride Islands in Carbon Materials for Efficient Electrochemical Synthesis of Hydrogen Peroxide. United States. https://doi.org/10.1021/jacs.8b02798
Chen, Shucheng, Chen, Zhihua, Siahrostami, Samira, Higgins, Drew, Nordlund, Dennis, Sokaras, Dimosthenis, Kim, Taeho Roy, Liu, Yunzhi, Yan, Xuzhou, Nilsson, Elisabeth, Sinclair, Robert, Norskov, Jens K., Jaramillo, Thomas F., and Bao, Zhenan. Wed . "Designing Boron Nitride Islands in Carbon Materials for Efficient Electrochemical Synthesis of Hydrogen Peroxide". United States. https://doi.org/10.1021/jacs.8b02798. https://www.osti.gov/servlets/purl/1459647.
@article{osti_1459647,
title = {Designing Boron Nitride Islands in Carbon Materials for Efficient Electrochemical Synthesis of Hydrogen Peroxide},
author = {Chen, Shucheng and Chen, Zhihua and Siahrostami, Samira and Higgins, Drew and Nordlund, Dennis and Sokaras, Dimosthenis and Kim, Taeho Roy and Liu, Yunzhi and Yan, Xuzhou and Nilsson, Elisabeth and Sinclair, Robert and Norskov, Jens K. and Jaramillo, Thomas F. and Bao, Zhenan},
abstractNote = {Heteroatom-doped carbons have drawn increasing research interest as catalysts for various electrochemical reactions due to their unique electronic and surface structures. In particular, co-doping of carbon with boron and nitrogen has been shown to provide significant catalytic activity for oxygen reduction reaction (ORR). However, limited experimental work has been done to systematically study these materials, and much remains to be understood about the nature of the active site(s), particularly with regards to the factors underlying the activity enhancements of these boron–carbon–nitrogen (BCN) materials. Herein, we prepare several BCN materials experimentally with a facile and controlled synthesis method, and systematically study their electrochemical performance. We demonstrate the existence of h-BN domains embedded in the graphitic structures of these materials using X-ray spectroscopy. These synthesized structures yield higher activity and selectivity toward the 2e– ORR to H2O2 than structures with individual B or N doping. We further employ density functional theory calculations to understand the role of a variety of h-BN domains within the carbon lattice for the ORR and find that the interface between h-BN domains and graphene exhibits unique catalytic behavior that can preferentially drive the production of H2O2. Here, to the best of our knowledge, this is the first example of h-BN domains in carbon identified as a novel system for the electrochemical production of H2O2.},
doi = {10.1021/jacs.8b02798},
journal = {Journal of the American Chemical Society},
number = 25,
volume = 140,
place = {United States},
year = {2018},
month = {6}
}

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Figures / Tables:

Figure 1 Figure 1: (a) A schematic of the BCN configuration models examined in this study. Color code: C(gray), N(blue), B(pink). %X composition is defined as the number of Catoms substituted in $h$-BN substrate over the total number of substrate atoms. Similarly, for BN domains %X composition is defined as the numbermore » of BN pairs substituted in graphene substrate over the total number of substrate atoms. (b) Theoretical activity volcano maps for two- (red) and four- (black) electron reduction of O2 to hydrogen peroxide and water, respectively. Both volcano plots are based on the RHE scale. The equilibrium potentials for both two- and four-electron ORR are shown as dashed red and black lines, respectively. Triangles or diamonds represent the activity of the N- or B-doped in the pristine (N-Gr or B-Gr) and defect (N-Gr-D or B-Gr-D) graphene, respectively. The activity of N-Gr-D is adapted from Ref. [34] while the activity of Pt(111) and PtHg4 alloy are adapted from Refs. [37], and [24], respectively.« less

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Works referenced in this record:

Thermal conductivity of BN-C nanostructures
journal, September 2012


Metal-Free Catalysts for Oxygen Reduction Reaction
journal, May 2015

  • Dai, Liming; Xue, Yuhua; Qu, Liangti
  • Chemical Reviews, Vol. 115, Issue 11
  • DOI: 10.1021/cr5003563

Energetics and kinetics of vacancies in monolayer graphene boron nitride heterostructures
journal, December 2014


Metal-Free Carbon Materials for CO 2 Electrochemical Reduction
journal, September 2017


Disorder and Segregation in B−C−N Graphene-Type Layers and Nanotubes: Tuning the Band Gap
journal, December 2010

  • da Rocha Martins, Jonathan; Chacham, Hélio
  • ACS Nano, Vol. 5, Issue 1
  • DOI: 10.1021/nn101809j

The application of graphene and its composites in oxygen reduction electrocatalysis: a perspective and review of recent progress
journal, January 2016

  • Higgins, Drew; Zamani, Pouyan; Yu, Aiping
  • Energy & Environmental Science, Vol. 9, Issue 2
  • DOI: 10.1039/C5EE02474A

Ultrasoft pseudopotentials and projector augmented-wave data sets: application to diatomic molecules
journal, October 2011


Ab initio study of the interactions between boron and nitrogen dopants in graphene
journal, August 2012

  • Al-Aqtash, Nabil; Al-Tarawneh, Khaldoun M.; Tawalbeh, Tarek
  • Journal of Applied Physics, Vol. 112, Issue 3
  • DOI: 10.1063/1.4742063

Atomic layers of hybridized boron nitride and graphene domains
journal, February 2010

  • Ci, Lijie; Song, Li; Jin, Chuanhong
  • Nature Materials, Vol. 9, Issue 5, p. 430-435
  • DOI: 10.1038/nmat2711

Tunable Electronics in Large-Area Atomic Layers of Boron–Nitrogen–Carbon
journal, July 2013

  • Muchharla, Baleeswaraiah; Pathak, Arjun; Liu, Zheng
  • Nano Letters, Vol. 13, Issue 8
  • DOI: 10.1021/nl400721y

Performing Mathematical Operations with Metamaterials
journal, January 2014


Three-Dimensional Nitrogen and Boron Co-doped Graphene for High-Performance All-Solid-State Supercapacitors
journal, July 2012

  • Wu, Zhong-Shuai; Winter, Andreas; Chen, Long
  • Advanced Materials, Vol. 24, Issue 37
  • DOI: 10.1002/adma.201201948

Sustainable Synthesis and Assembly of Biomass-Derived B/N Co-Doped Carbon Nanosheets with Ultrahigh Aspect Ratio for High-Performance Supercapacitors
journal, November 2015

  • Ling, Zheng; Wang, Zhiyu; Zhang, Mengdi
  • Advanced Functional Materials, Vol. 26, Issue 1
  • DOI: 10.1002/adfm.201504004

Superior performance of borocarbonitrides, B x C y N z , as stable, low-cost metal-free electrocatalysts for the hydrogen evolution reaction
journal, January 2016

  • Chhetri, Manjeet; Maitra, Somak; Chakraborty, Himanshu
  • Energy Environ. Sci., Vol. 9, Issue 1
  • DOI: 10.1039/C5EE02521D

Carbon-doped BN nanosheets for metal-free photoredox catalysis
journal, July 2015

  • Huang, Caijin; Chen, Cheng; Zhang, Mingwen
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8698

Selective Electrochemical Reduction of Carbon Dioxide to Ethanol on a Boron- and Nitrogen-Co-doped Nanodiamond
journal, October 2017

  • Liu, Yanming; Zhang, Yujing; Cheng, Kai
  • Angewandte Chemie International Edition, Vol. 56, Issue 49
  • DOI: 10.1002/anie.201706311

Can Boron and Nitrogen Co-doping Improve Oxygen Reduction Reaction Activity of Carbon Nanotubes?
journal, January 2013

  • Zhao, Yu; Yang, Lijun; Chen, Sheng
  • Journal of the American Chemical Society, Vol. 135, Issue 4
  • DOI: 10.1021/ja310566z

BCN Graphene as Efficient Metal-Free Electrocatalyst for the Oxygen Reduction Reaction
journal, March 2012

  • Wang, Shuangyin; Zhang, Lipeng; Xia, Zhenhai
  • Angewandte Chemie International Edition, Vol. 51, Issue 17
  • DOI: 10.1002/anie.201109257

Efficient Metal-Free Electrocatalysts for Oxygen Reduction: Polyaniline-Derived N- and O-Doped Mesoporous Carbons
journal, May 2013

  • Silva, Rafael; Voiry, Damien; Chhowalla, Manish
  • Journal of the American Chemical Society, Vol. 135, Issue 21
  • DOI: 10.1021/ja402450a

Effect of boron–nitrogen bonding on oxygen reduction reaction activity of BN Co-doped activated porous carbons
journal, January 2015


Vertically Aligned BCN Nanotubes as Efficient Metal-Free Electrocatalysts for the Oxygen Reduction Reaction: A Synergetic Effect by Co-Doping with Boron and Nitrogen
journal, October 2011

  • Wang , Shuangyin; Iyyamperumal , Eswaramoorthi; Roy, Ajit
  • Angewandte Chemie International Edition, Vol. 50, Issue 49
  • DOI: 10.1002/anie.201105204

Hydrogen Peroxide Synthesis: An Outlook beyond the Anthraquinone Process
journal, October 2006

  • Campos-Martin, Jose M.; Blanco-Brieva, Gema; Fierro, Jose L. G.
  • Angewandte Chemie International Edition, Vol. 45, Issue 42
  • DOI: 10.1002/anie.200503779

Unifying the 2e and 4e Reduction of Oxygen on Metal Surfaces
journal, September 2012

  • Viswanathan, Venkatasubramanian; Hansen, Heine Anton; Rossmeisl, Jan
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 20
  • DOI: 10.1021/jz301476w

Enabling direct H2O2 production through rational electrocatalyst design
journal, November 2013

  • Siahrostami, Samira; Verdaguer-Casadevall, Arnau; Karamad, Mohammadreza
  • Nature Materials, Vol. 12, Issue 12
  • DOI: 10.1038/nmat3795

Structural effects in electrocatalysis
journal, May 1984

  • Marković, N. M.; Adić, R. R.; Vešović, V. B.
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 165, Issue 1-2
  • DOI: 10.1016/S0022-0728(84)80091-1

Trends in the Electrochemical Synthesis of H 2 O 2 : Enhancing Activity and Selectivity by Electrocatalytic Site Engineering
journal, February 2014

  • Verdaguer-Casadevall, Arnau; Deiana, Davide; Karamad, Mohammadreza
  • Nano Letters, Vol. 14, Issue 3
  • DOI: 10.1021/nl500037x

Single Atom Hot-Spots at Au–Pd Nanoalloys for Electrocatalytic H 2 O 2 Production
journal, December 2011

  • Jirkovský, Jakub S.; Panas, Itai; Ahlberg, Elisabet
  • Journal of the American Chemical Society, Vol. 133, Issue 48
  • DOI: 10.1021/ja206477z

Highly Selective Two-Electron Oxygen Reduction Catalyzed by Mesoporous Nitrogen-Doped Carbon
journal, September 2014

  • Park, Jisung; Nabae, Yuta; Hayakawa, Teruaki
  • ACS Catalysis, Vol. 4, Issue 10
  • DOI: 10.1021/cs5008206

High-Yield Electrosynthesis of Hydrogen Peroxide from Oxygen Reduction by Hierarchically Porous Carbon
journal, April 2015

  • Liu, Yanming; Quan, Xie; Fan, Xinfei
  • Angewandte Chemie International Edition, Vol. 54, Issue 23
  • DOI: 10.1002/anie.201502396

Novel synthesis of N-doped porous carbons from collagen for electrocatalytic production of H2O2
journal, September 2012


Mesoporous Nitrogen-Doped Carbon for the Electrocatalytic Synthesis of Hydrogen Peroxide
journal, February 2012

  • Fellinger, Tim-Patrick; Hasché, Frédéric; Strasser, Peter
  • Journal of the American Chemical Society, Vol. 134, Issue 9
  • DOI: 10.1021/ja300038p

Development of a reactor with carbon catalysts for modular-scale, low-cost electrochemical generation of H 2 O 2
journal, January 2017

  • Chen, Zhihua; Chen, Shucheng; Siahrostami, Samira
  • Reaction Chemistry & Engineering, Vol. 2, Issue 2
  • DOI: 10.1039/C6RE00195E

Defective Carbon-Based Materials for the Electrochemical Synthesis of Hydrogen Peroxide
journal, November 2017


Ultrahigh Surface Area Three-Dimensional Porous Graphitic Carbon from Conjugated Polymeric Molecular Framework
journal, May 2015


Hierarchical nanostructured conducting polymer hydrogel with high electrochemical activity
journal, May 2012

  • Pan, L.; Yu, G.; Zhai, D.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 24
  • DOI: 10.1073/pnas.1202636109

Highly Cross-Linked, Self-Doped Polyaniline Exhibiting Unprecedented Hardness
journal, July 2005

  • Deore, Bhavana A.; Yu, Insun; Aguiar, Pedro M.
  • Chemistry of Materials, Vol. 17, Issue 15
  • DOI: 10.1021/cm0505392

Atomistic Interrogation of B–N Co-dopant Structures and Their Electronic Effects in Graphene
journal, June 2016


π * and σ * Excitons in C 1 s Absorption of Graphite
journal, January 1995


Investigating the structure of boron nitride nanotubes by near-edge X-ray absorption fine structure (NEXAFS) spectroscopy
journal, January 2005

  • Hemraj-Benny, Tirandai; BanerjeeCurrent address: Department, Sarbajit; Sambasivan, Sharadha
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 6
  • DOI: 10.1039/b415423a

Evidence for the existence of nitrogen-substituted graphite structure by polarization dependence of near-edge x-ray-absorption fine structure
journal, September 2000


Connecting Dopant Bond Type with Electronic Structure in N-Doped Graphene
journal, July 2012

  • Schiros, Theanne; Nordlund, Dennis; Pálová, Lucia
  • Nano Letters, Vol. 12, Issue 8
  • DOI: 10.1021/nl301409h

High-performance oxygen reduction and evolution carbon catalysis: From mechanistic studies to device integration
journal, November 2016


Active sites of nitrogen-doped carbon materials for oxygen reduction reaction clarified using model catalysts
journal, January 2016


pH dependence of catalytic activity for ORR of the non-PGM catalyst derived from heat-treated Fe–phenanthroline
journal, January 2013


Unifying Kinetic and Thermodynamic Analysis of 2 e and 4 e Reduction of Oxygen on Metal Surfaces
journal, March 2014

  • Hansen, Heine A.; Viswanathan, Venkatasubramanian; Nørskov, Jens K.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 13
  • DOI: 10.1021/jp4100608

Interplay between nitrogen dopants and native point defects in graphene
journal, April 2012


Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode
journal, November 2004

  • Nørskov, J. K.; Rossmeisl, J.; Logadottir, A.
  • The Journal of Physical Chemistry B, Vol. 108, Issue 46
  • DOI: 10.1021/jp047349j

Works referencing / citing this record:

Synergetic effect of pyrrolic-N and doped boron in mesoporous carbon for electrocatalytic ozone production
journal, January 2020

  • Zhang, Qiaoqiao; Cao, Yongyong; Yan, Yilong
  • Journal of Materials Chemistry A, Vol. 8, Issue 5
  • DOI: 10.1039/c9ta12866b

Defective graphene domains in boron nitride sheets
journal, July 2019

  • dos Santos, Ramiro Marcelo; Santos, Renato Batista; Neto, Bernahrd Georg Enders
  • Journal of Molecular Modeling, Vol. 25, Issue 8
  • DOI: 10.1007/s00894-019-4093-5

Active Edge‐Site‐Rich Carbon Nanocatalysts with Enhanced Electron Transfer for Efficient Electrochemical Hydrogen Peroxide Production
journal, January 2019

  • Sa, Young Jin; Kim, Jae Hyung; Joo, Sang Hoon
  • Angewandte Chemie International Edition, Vol. 58, Issue 4
  • DOI: 10.1002/anie.201812435

Highly selective oxygen reduction to hydrogen peroxide on transition metal single atom coordination
journal, September 2019


Under-cover stabilization and reactivity of a dense carbon monoxide layer on Pt(111)
journal, January 2019

  • Píš, Igor; Magnano, Elena; Nappini, Silvia
  • Chemical Science, Vol. 10, Issue 6
  • DOI: 10.1039/c8sc04461a

Atomic-level tuning of Co–N–C catalyst for high-performance electrochemical H2O2 production
journal, January 2020


Progress Towards Direct Hydrogen Peroxide Fuel Cells (DHPFCs) as an Energy Storage Concept
journal, January 2018

  • McDonnell-Worth, Ciaran J.; MacFarlane, Douglas R.
  • Australian Journal of Chemistry, Vol. 71, Issue 10
  • DOI: 10.1071/ch18328

Photo-enhanced Zn–air batteries with simultaneous highly efficient in situ H 2 O 2 generation for wastewater treatment
journal, January 2019

  • Wang, Kun; Mo, Zhuohua; Tang, Songtao
  • Journal of Materials Chemistry A, Vol. 7, Issue 23
  • DOI: 10.1039/c9ta04253a

Copolymer‐Derived N/B Co‐Doped Nanocarbons with Controlled Porosity and Highly Active Surface
journal, October 2019

  • Yuan, Rui; Wang, Han; Sun, Mingkang
  • Journal of Polymer Science, Vol. 58, Issue 1
  • DOI: 10.1002/pol.20190002

Hydrogen peroxide synthesis on porous graphitic carbon nitride using water as a hydrogen source
journal, January 2020

  • Cao, Yongyong; Zhou, Guobing; Chen, Xianlang
  • Journal of Materials Chemistry A, Vol. 8, Issue 1
  • DOI: 10.1039/c9ta08103h

Selective Electrochemical H 2 O 2 Production through Two-Electron Oxygen Electrochemistry
journal, September 2018

  • Jiang, Yuanyuan; Ni, Pengjuan; Chen, Chuanxia
  • Advanced Energy Materials, Vol. 8, Issue 31
  • DOI: 10.1002/aenm.201801909

Fluorescent Carbon‐ and Oxygen‐Doped Hexagonal Boron Nitride Powders as Printing Ink for Anticounterfeit Applications
journal, September 2019

  • Liu, Feng; Nattestad, Andrew; Naficy, Sina
  • Advanced Optical Materials, Vol. 7, Issue 24
  • DOI: 10.1002/adom.201901380

Active Edge‐Site‐Rich Carbon Nanocatalysts with Enhanced Electron Transfer for Efficient Electrochemical Hydrogen Peroxide Production
journal, December 2018

  • Sa, Young Jin; Kim, Jae Hyung; Joo, Sang Hoon
  • Angewandte Chemie, Vol. 131, Issue 4
  • DOI: 10.1002/ange.201812435

Direct electrosynthesis of pure aqueous H 2 O 2 solutions up to 20% by weight using a solid electrolyte
journal, October 2019


Electrochemical synthesis of hydrogen peroxide from water and oxygen
journal, June 2019

  • Perry, Samuel C.; Pangotra, Dhananjai; Vieira, Luciana
  • Nature Reviews Chemistry, Vol. 3, Issue 7
  • DOI: 10.1038/s41570-019-0110-6

Vacancy in Ultrathin 2D Nanomaterials toward Sustainable Energy Application
journal, November 2019

  • Bai, Fan; Xu, Liang; Zhai, Xiaoying
  • Advanced Energy Materials, Vol. 10, Issue 11
  • DOI: 10.1002/aenm.201902107

Tailoring the Electrochemical Production of H 2 O 2 : Strategies for the Rational Design of High‐Performance Electrocatalysts
journal, September 2019


A COOH-terminated nitrogen-doped carbon aerogel as a bulk electrode for completely selective two-electron oxygen reduction to H 2 O 2
journal, January 2019

  • Zhao, Hongying; Shen, Xuqian; Chen, Ying
  • Chemical Communications, Vol. 55, Issue 44
  • DOI: 10.1039/c9cc02580d

Hydrogen peroxide electrochemical synthesis on hybrid double-atom (Pd–Cu) doped N vacancy g-C 3 N 4 : a novel design strategy for electrocatalyst screening
journal, January 2020

  • Cao, Yongyong; Zhao, Chenxia; Fang, Qiaojun
  • Journal of Materials Chemistry A, Vol. 8, Issue 5
  • DOI: 10.1039/c9ta12468c

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