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Title: Nature-Derived Approach to Oxygen and Chlorine Dual-Vacancies for Efficient Photocatalysis and Photoelectrochemistry

Abstract

Crystal defect engineering has sparked huge interests owing to their significance for tailoring surface properties, photoelectronic properties, etc. However, conventional methods, e.g., H2 reduction, can only achieve a single type of vacancy and always suffer from the drawbacks of harsh synthetic condition, complex procedure, and energy consuming. In this paper, we report a green, cost-effective, and scalable nature-derived reduction protocol with extracting solution of green tea and spinach to in situ achieve oxygen and chlorine dual-vacancies in BiOCl (BiO1–xCl1-y). The introduction of O and Cl vacancies gives rise to enormous amelioration on the crystal structure, electronic band structure, and surface state, thereby resulting in enhanced photoabsorption and a remarkably enhanced surface charge transfer efficiency (11-fold enhancement). Profiting from these merits, BiO1–xCl1–y exhibits highly promoted photocatalytic oxidation ability and an efficient activity for selective CO2 reduction into CO. Interestingly, continuously adjustable photoresponse and defect level for BiO1–xCl1–y was realized by simply regulating the extract concentration, which can well balance photoabsorption and photoredox driving force. The current synthetic route is demonstrated to be also applicable to BiOBr and BiOI. To verify the role of the current natural antioxidant, BiO1–xCl1–y is also successfully synthesized by the chemicals of extracting solution ingredients. This workmore » exclusively sheds new light on engineering crystal defects via the eco-friendly bioinspired tactics and also provides a reference for promoting photo (electro) chemical property by dual-vacancies cooperation.« less

Authors:
 [1]; ORCiD logo [1];  [1];  [2]; ORCiD logo [3]; ORCiD logo [4];  [1]; ORCiD logo [1]
  1. China Univ. of Geosciences, Beijing (China)
  2. Univ. of Nevada, Las Vegas, NV (United States)
  3. Chongqing Technology and Business Univ., Chongqing (China)
  4. Nanyang Normal Univ., Nanyang (China)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
National Natural Science Foundation of China (NSFC); USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES); Fundamental Research Funds for the Central Universities
OSTI Identifier:
1419879
Resource Type:
Accepted Manuscript
Journal Name:
ACS Sustainable Chemistry & Engineering
Additional Journal Information:
Journal Volume: 6; Journal Issue: 2; Journal ID: ISSN 2168-0485
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; BiO1−xCl1−y; Vacancy; Green tea; Spinach; Photocatalysis

Citation Formats

Li, Min, Zhang, Yihe, Li, Xiaowei, Wang, Yonggang, Dong, Fan, Ye, Liqun, Yu, Shixin, and Huang, Hongwei. Nature-Derived Approach to Oxygen and Chlorine Dual-Vacancies for Efficient Photocatalysis and Photoelectrochemistry. United States: N. p., 2018. Web. doi:10.1021/acssuschemeng.7b03847.
Li, Min, Zhang, Yihe, Li, Xiaowei, Wang, Yonggang, Dong, Fan, Ye, Liqun, Yu, Shixin, & Huang, Hongwei. Nature-Derived Approach to Oxygen and Chlorine Dual-Vacancies for Efficient Photocatalysis and Photoelectrochemistry. United States. https://doi.org/10.1021/acssuschemeng.7b03847
Li, Min, Zhang, Yihe, Li, Xiaowei, Wang, Yonggang, Dong, Fan, Ye, Liqun, Yu, Shixin, and Huang, Hongwei. Tue . "Nature-Derived Approach to Oxygen and Chlorine Dual-Vacancies for Efficient Photocatalysis and Photoelectrochemistry". United States. https://doi.org/10.1021/acssuschemeng.7b03847. https://www.osti.gov/servlets/purl/1419879.
@article{osti_1419879,
title = {Nature-Derived Approach to Oxygen and Chlorine Dual-Vacancies for Efficient Photocatalysis and Photoelectrochemistry},
author = {Li, Min and Zhang, Yihe and Li, Xiaowei and Wang, Yonggang and Dong, Fan and Ye, Liqun and Yu, Shixin and Huang, Hongwei},
abstractNote = {Crystal defect engineering has sparked huge interests owing to their significance for tailoring surface properties, photoelectronic properties, etc. However, conventional methods, e.g., H2 reduction, can only achieve a single type of vacancy and always suffer from the drawbacks of harsh synthetic condition, complex procedure, and energy consuming. In this paper, we report a green, cost-effective, and scalable nature-derived reduction protocol with extracting solution of green tea and spinach to in situ achieve oxygen and chlorine dual-vacancies in BiOCl (BiO1–xCl1-y). The introduction of O and Cl vacancies gives rise to enormous amelioration on the crystal structure, electronic band structure, and surface state, thereby resulting in enhanced photoabsorption and a remarkably enhanced surface charge transfer efficiency (11-fold enhancement). Profiting from these merits, BiO1–xCl1–y exhibits highly promoted photocatalytic oxidation ability and an efficient activity for selective CO2 reduction into CO. Interestingly, continuously adjustable photoresponse and defect level for BiO1–xCl1–y was realized by simply regulating the extract concentration, which can well balance photoabsorption and photoredox driving force. The current synthetic route is demonstrated to be also applicable to BiOBr and BiOI. To verify the role of the current natural antioxidant, BiO1–xCl1–y is also successfully synthesized by the chemicals of extracting solution ingredients. This work exclusively sheds new light on engineering crystal defects via the eco-friendly bioinspired tactics and also provides a reference for promoting photo (electro) chemical property by dual-vacancies cooperation.},
doi = {10.1021/acssuschemeng.7b03847},
journal = {ACS Sustainable Chemistry & Engineering},
number = 2,
volume = 6,
place = {United States},
year = {Tue Jan 09 00:00:00 EST 2018},
month = {Tue Jan 09 00:00:00 EST 2018}
}

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Works referenced in this record:

Solar Synthesis: Prospects in Visible Light Photocatalysis
journal, February 2014


From UV to Near-Infrared, WS 2 Nanosheet: A Novel Photocatalyst for Full Solar Light Spectrum Photodegradation
journal, November 2014

  • Sang, Yuanhua; Zhao, Zhenhuan; Zhao, Mingwen
  • Advanced Materials, Vol. 27, Issue 2
  • DOI: 10.1002/adma.201403264

Template-free precursor-surface-etching route to porous, thin g-C 3 N 4 nanosheets for enhancing photocatalytic reduction and oxidation activity
journal, January 2017

  • Huang, Hongwei; Xiao, Ke; Tian, Na
  • Journal of Materials Chemistry A, Vol. 5, Issue 33
  • DOI: 10.1039/C7TA04639A

Large Scaled Synthesis of Heterostructured Electrospun TiO 2 /SnO 2 Nanofibers with an Enhanced Photocatalytic Activity
journal, January 2017

  • Zhang, Li; Yu, Wei; Han, Cui
  • Journal of The Electrochemical Society, Vol. 164, Issue 9
  • DOI: 10.1149/2.1531709jes

Heterostructured TiO 2 /WO 3 Nanocomposites for Photocatalytic Degradation of Toluene under Visible Light
journal, January 2017

  • Zhang, Li; Qin, Mingke; Yu, Wei
  • Journal of The Electrochemical Society, Vol. 164, Issue 14
  • DOI: 10.1149/2.0881714jes

Vacancy Associates Promoting Solar-Driven Photocatalytic Activity of Ultrathin Bismuth Oxychloride Nanosheets
journal, May 2013

  • Guan, Meili; Xiao, Chong; Zhang, Jie
  • Journal of the American Chemical Society, Vol. 135, Issue 28
  • DOI: 10.1021/ja402956f

Crystal Structure Modification Enhanced FeNb 11 O 29 Anodes for Lithium-Ion Batteries
journal, September 2017


Nano-TiNb2O7/carbon nanotubes composite anode for enhanced lithium-ion storage
journal, January 2018


Enhanced photocatalytic activity of Bi2WO6 with oxygen vacancies by zirconium doping
journal, November 2011


Controlled synthesis of a highly dispersed BiPO 4 photocatalyst with surface oxygen vacancies
journal, January 2015


Fabrication of Wide–Range–Visible Photocatalyst Bi2WO6−x nanoplates via Surface Oxygen Vacancies
journal, January 2016

  • Lv, Yanhui; Yao, Wenqing; Zong, Ruilong
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep19347

Increasing visible-light absorption for photocatalysis with black BiOCl
journal, January 2012

  • Ye, Liqun; Deng, Kejian; Xu, Feng
  • Phys. Chem. Chem. Phys., Vol. 14, Issue 1
  • DOI: 10.1039/C1CP22876E

Oxygen Vacancy Induced Bismuth Oxyiodide with Remarkably Increased Visible-Light Absorption and Superior Photocatalytic Performance
journal, December 2014

  • Huang, Yongchao; Li, Haibo; Balogun, Muhammad-Sadeeq
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 24
  • DOI: 10.1021/am507641k

Preparation of black BiOCl with visible light photocatalytic activity by Fe reduction
journal, February 2014


Polyaniline-Decorated {001} Facets of Bi 2 O 2 CO 3 Nanosheets: In Situ Oxygen Vacancy Formation and Enhanced Visible Light Photocatalytic Activity
journal, December 2014

  • Zhao, Ziyan; Zhou, Ying; Wang, Fang
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 1
  • DOI: 10.1021/am507089x

Facile Synthesis of Defective TiO2−x Nanocrystals with High Surface Area and Tailoring Bandgap for Visible-light Photocatalysis
journal, October 2015

  • Wajid Shah, Muhammad; Zhu, Yunqing; Fan, Xiaoyun
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep15804

New Reaction Pathway Induced by Plasmon for Selective Benzyl Alcohol Oxidation on BiOCl Possessing Oxygen Vacancies
journal, February 2017

  • Li, Hao; Qin, Feng; Yang, Zhiping
  • Journal of the American Chemical Society, Vol. 139, Issue 9
  • DOI: 10.1021/jacs.6b12850

Synthesis and Facet-Dependent Photoreactivity of BiOCl Single-Crystalline Nanosheets
journal, March 2012

  • Jiang, Jing; Zhao, Kun; Xiao, Xiaoyi
  • Journal of the American Chemical Society, Vol. 134, Issue 10
  • DOI: 10.1021/ja210484t

Giant Enhancement of Internal Electric Field Boosting Bulk Charge Separation for Photocatalysis
journal, March 2016


Solar-Light-Driven Pure Water Splitting with Ultrathin BiOCl Nanosheets
journal, October 2015

  • Zhang, Ling; Han, Zhongkang; Wang, Wenzhong
  • Chemistry - A European Journal, Vol. 21, Issue 50
  • DOI: 10.1002/chem.201503778

Green synthesis of iron nanoparticles and their application as a Fenton-like catalyst for the degradation of aqueous cationic and anionic dyes
journal, August 2011


Green production of zero-valent iron nanoparticles using tree leaf extracts
journal, February 2013


Biosynthesis of Iron and Silver Nanoparticles at Room Temperature Using Aqueous Sorghum Bran Extracts
journal, January 2011

  • Njagi, Eric C.; Huang, Hui; Stafford, Lisa
  • Langmuir, Vol. 27, Issue 1
  • DOI: 10.1021/la103190n

Chemiluminescence assay for catechin based on generation of hydrogen peroxide in basic solution
journal, November 2002


Oxygen Vacancy Structure Associated Photocatalytic Water Oxidation of BiOCl
journal, November 2016


Superior visible light hydrogen evolution of Janus bilayer junctions via atomic-level charge flow steering
journal, May 2016

  • Li, Jie; Zhan, Guangming; Yu, Ying
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms11480

Synthesis of black ultrathin BiOCl nanosheets for efficient photocatalytic H2 production under visible light irradiation
journal, October 2015


Insights into the photosensitivity activity of BiOCl under visible light irradiation
journal, October 2014


Synthesis of a Highly Efficient BiOCl Single-Crystal Nanodisk Photocatalyst with Exposing {001} Facets
journal, May 2014

  • Zhang, Xing; Wang, Xin-Bo; Wang, Li-Wei
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 10
  • DOI: 10.1021/am5010392

Oxygen vacancies contained TiO2 spheres: facile fabrication and enhanced ferromagnetism
journal, July 2012

  • Li, Hongmei; Zeng, Yangsu; Huang, Tongcheng
  • Journal of Nanoparticle Research, Vol. 14, Issue 8
  • DOI: 10.1007/s11051-012-1030-2

An Insight into the Role of Oxygen Vacancy in Hydrogenated TiO 2 Nanocrystals in the Performance of Dye-Sensitized Solar Cells
journal, February 2015

  • Su, Ting; Yang, Yulin; Na, Yong
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 6
  • DOI: 10.1021/am5085447

Fe-ions modified mesoporous Bi2WO6 nanosheets with high visible light photocatalytic activity
journal, March 2012

  • Guo, Sen; Li, Xiaofang; Wang, Haiqiang
  • Journal of Colloid and Interface Science, Vol. 369, Issue 1
  • DOI: 10.1016/j.jcis.2011.12.007

UV-resistant superhydrophobic BiOCl nanoflake film by a room-temperature hydrolysis process
journal, January 2011

  • Li, Yuanyuan; Liu, Jinping; Jiang, Jian
  • Dalton Transactions, Vol. 40, Issue 25
  • DOI: 10.1039/c1dt10691k

Photoreduction of CO2 on BiOCl nanoplates with the assistance of photoinduced oxygen vacancies
journal, September 2014


Self-doping and surface plasmon modification induced visible light photocatalysis of BiOCl
journal, January 2013


Selective transport of electron and hole among {0 0 1} and {1 1 0} facets of BiOCl for pure water splitting
journal, January 2015


An Elemental Phosphorus Photocatalyst with a Record High Hydrogen Evolution Efficiency
journal, May 2016

  • Hu, Zhuofeng; Yuan, Luyan; Liu, Zhifeng
  • Angewandte Chemie International Edition, Vol. 55, Issue 33
  • DOI: 10.1002/anie.201603331

In-depth insight into facet-dependent charge movement behaviors and photo-redox catalysis: A case of {0 0 1} and {0 1 0} facets BiOCl
journal, December 2017


Macroscopic Polarization Enhancement Promoting Photo- and Piezoelectric-Induced Charge Separation and Molecular Oxygen Activation
journal, August 2017

  • Huang, Hongwei; Tu, Shuchen; Zeng, Chao
  • Angewandte Chemie International Edition, Vol. 56, Issue 39
  • DOI: 10.1002/anie.201706549

Exciton-Free, Nonsensitized Degradation of 2-Naphthol by Facet-Dependent BiOCl under Visible Light: Novel Evidence of Surface-State Photocatalysis
journal, November 2013

  • Weng, Sunxian; Pei, ZengXia; Zheng, Zuyang
  • ACS Applied Materials & Interfaces, Vol. 5, Issue 23
  • DOI: 10.1021/am403214r

Oxygen Vacancy Associated Surface Fenton Chemistry: Surface Structure Dependent Hydroxyl Radicals Generation and Substrate Dependent Reactivity
journal, April 2017

  • Li, Hao; Shang, Jian; Yang, Zhiping
  • Environmental Science & Technology, Vol. 51, Issue 10
  • DOI: 10.1021/acs.est.7b00040

Photochemistry of Hydrochar: Reactive Oxygen Species Generation and Sulfadimidine Degradation
journal, September 2017

  • Chen, Na; Huang, Yahui; Hou, Xiaojing
  • Environmental Science & Technology, Vol. 51, Issue 19
  • DOI: 10.1021/acs.est.7b02740

The effect of oxygen vacancies on the photocatalytic activity of BiOCl nanocrystals prepared by hydrolysis and UV light irradiation
journal, September 2014

  • Sarwan, Bhawna; Pare, Brijesh; Acharya, A. D.
  • Materials Science in Semiconductor Processing, Vol. 25
  • DOI: 10.1016/j.mssp.2013.09.015

Works referencing / citing this record:

Defect Engineering of Photocatalysts for Solar Energy Conversion
journal, April 2020


Atomic‐Level Reactive Sites for Semiconductor‐Based Photocatalytic CO 2 Reduction
journal, January 2020

  • Zhang, Yanzhao; Xia, Bingquan; Ran, Jingrun
  • Advanced Energy Materials, Vol. 10, Issue 9
  • DOI: 10.1002/aenm.201903879