p-Type BP nanosheet photocatalyst with AQE of 3.9% in the absence of a noble metal cocatalyst: investigation and elucidation of photophysical properties

Rahman, Mohammad Z.; Batmunkh, Munkhbayar; Bat-Erdene, Munkhjargal; Shapter, Joseph G.; Mullins, C. Buddie

doi:10.1039/c8ta07034b

Title: p-Type BP nanosheet photocatalyst with AQE of 3.9% in the absence of a noble metal cocatalyst: investigation and elucidation of photophysical properties

Abstract

While stability, significantly poor apparent quantum efficiency (AQE < 0.5%) and over dependence on noble metal cocatalysts is a long standing problem, here, we report, for the first time, microwave-exfoliated p-type few-layer black phosphorous (BP-nanosheets) as a stable photocatalyst for hydrogen production without any supporting noble metal co-catalyst. This few layer BP has shown a record high apparent quantum efficiency (AQE) of ~4% at 420 nm under visible light irradiation. This unprecedented AQE stems from a low level of material oxidation that impedes the degradation of BP under ambient conditions, strong absorption of photons at the surface, and a conduction band edge position that favorably facilitates the proton reduction reaction. These BP-nanosheets have also shown superior photocatalytic performance compared to the known cohort of metal-free photocatalysts such as graphitic carbon nitride, carbon dots, and red-P under identical experimental conditions. An understanding of the photo-physicochemical reasons that drive this chemistry is elucidated along with results obtained from physicochemical characterization and finite difference time domain simulations.

Authors:

^[1]; Batmunkh, Munkhbayar ^[2]; Bat-Erdene, Munkhjargal ^[2];

^[2];

^[3]

Univ. of Adelaide, SA (Australia); Univ. of Texas, Austin, TX (United States)
Univ. of Queensland, Brisbane, QLD (Australia); Flinders Univ., Adelaide, SA (Australia)
Univ. of Texas, Austin, TX (United States)

Publication Date:: Sun Aug 05 00:00:00 EDT 2018

Research Org.:: Univ. of Texas, Austin, TX (United States)

Sponsoring Org.:: USDOE Office of Science (SC)

OSTI Identifier:: 1610669

Alternate Identifier(s):: OSTI ID: 1471268

Grant/Contract Number:: SC0002219; FG02-09ER16119

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Materials Chemistry. A

Additional Journal Information:: Journal Volume: 6; Journal Issue: 38; Journal ID: ISSN 2050-7488

Publisher:: Royal Society of Chemistry

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Energy & Fuels; Materials Science

Citation Formats


                    Rahman, Mohammad Z., Batmunkh, Munkhbayar, Bat-Erdene, Munkhjargal, Shapter, Joseph G., and Mullins, C. Buddie. p-Type BP nanosheet photocatalyst with AQE of 3.9% in the absence of a noble metal cocatalyst: investigation and elucidation of photophysical properties.  United States: N. p., 2018. 
Web.  doi:10.1039/c8ta07034b.

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                    Rahman, Mohammad Z., Batmunkh, Munkhbayar, Bat-Erdene, Munkhjargal, Shapter, Joseph G., & Mullins, C. Buddie. p-Type BP nanosheet photocatalyst with AQE of 3.9% in the absence of a noble metal cocatalyst: investigation and elucidation of photophysical properties.  United States.  https://doi.org/10.1039/c8ta07034b

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                    Rahman, Mohammad Z., Batmunkh, Munkhbayar, Bat-Erdene, Munkhjargal, Shapter, Joseph G., and Mullins, C. Buddie. Sun .  
"p-Type BP nanosheet photocatalyst with AQE of 3.9% in the absence of a noble metal cocatalyst: investigation and elucidation of photophysical properties".  United States.  https://doi.org/10.1039/c8ta07034b.  https://www.osti.gov/servlets/purl/1610669.

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@article{osti_1610669,

  title        = {p-Type BP nanosheet photocatalyst with AQE of 3.9% in the absence of a noble metal cocatalyst: investigation and elucidation of photophysical properties},

  author       = {Rahman, Mohammad Z. and Batmunkh, Munkhbayar and Bat-Erdene, Munkhjargal and Shapter, Joseph G. and Mullins, C. Buddie},

  abstractNote = {While stability, significantly poor apparent quantum efficiency (AQE < 0.5%) and over dependence on noble metal cocatalysts is a long standing problem, here, we report, for the first time, microwave-exfoliated p-type few-layer black phosphorous (BP-nanosheets) as a stable photocatalyst for hydrogen production without any supporting noble metal co-catalyst. This few layer BP has shown a record high apparent quantum efficiency (AQE) of ~4% at 420 nm under visible light irradiation. This unprecedented AQE stems from a low level of material oxidation that impedes the degradation of BP under ambient conditions, strong absorption of photons at the surface, and a conduction band edge position that favorably facilitates the proton reduction reaction. These BP-nanosheets have also shown superior photocatalytic performance compared to the known cohort of metal-free photocatalysts such as graphitic carbon nitride, carbon dots, and red-P under identical experimental conditions. An understanding of the photo-physicochemical reasons that drive this chemistry is elucidated along with results obtained from physicochemical characterization and finite difference time domain simulations.},

  doi          = {10.1039/c8ta07034b},

  journal      = {Journal of Materials Chemistry. A},

  number       = 38,

  volume       = 6,

  place        = {United States},

  year         = {Sun Aug 05 00:00:00 EDT 2018},

  month        = {Sun Aug 05 00:00:00 EDT 2018}

}

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Title: p-Type BP nanosheet photocatalyst with AQE of 3.9% in the absence of a noble metal cocatalyst: investigation and elucidation of photophysical properties

Abstract

Citation Formats

Heterogeneous photocatalyst materials for water splitting journal, January 2009

Electrochemical Photolysis of Water at a Semiconductor Electrode journal, July 1972

Two-dimensional material nanophotonics journal, November 2014

Strain Engineering for Phosphorene: The Potential Application as a Photocatalyst journal, November 2014

Carbon, nitrogen and phosphorus containing metal-free photocatalysts for hydrogen production: progress and challenges journal, January 2018

Powering the planet: Chemical challenges in solar energy utilization journal, October 2006

Black Phosphorus Nanosheets: Synthesis, Characterization and Applications journal, May 2016

Control of Surface and Edge Oxidation on Phosphorene journal, March 2017

α-Sulfur Crystals as a Visible-Light-Active Photocatalyst journal, May 2012

Red phosphorus: An elemental photocatalyst for hydrogen formation from water journal, January 2012

Rediscovering black phosphorus as an anisotropic layered material for optoelectronics and electronics journal, July 2014

Black Phosphorus: Synthesis and Application for Solar Cells journal, October 2017

Energy and environment policy case for a global project on artificial photosynthesis journal, January 2013

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A Benchmark Quantum Yield for Water Photoreduction on Amorphous Carbon Nitride journal, August 2017

Two-dimensional layered composite photocatalysts journal, January 2014

Production of few-layer phosphorene by liquid exfoliation of black phosphorus journal, January 2014

Expressway to partially oxidized phosphorene journal, April 2018

A metal-free polymeric photocatalyst for hydrogen production from water under visible light journal, November 2008

Phosphorene: An Unexplored 2D Semiconductor with a High Hole Mobility journal, March 2014

Interaction of Black Phosphorus with Oxygen and Water journal, November 2016

Hydrogen Production by Molecular Photocatalysis journal, October 2007

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Phosphorene as a Superior Gas Sensor: Selective Adsorption and Distinct I – V Response journal, July 2014

TiO 2 Photocatalysis: A Historical Overview and Future Prospects journal, December 2005

Black phosphorus field-effect transistors journal, March 2014

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journal, July 1972

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Strain Engineering for Phosphorene: The Potential Application as a Photocatalyst
journal, November 2014

Carbon, nitrogen and phosphorus containing metal-free photocatalysts for hydrogen production: progress and challenges
journal, January 2018

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Rediscovering black phosphorus as an anisotropic layered material for optoelectronics and electronics
journal, July 2014

Black Phosphorus: Synthesis and Application for Solar Cells
journal, October 2017

Energy and environment policy case for a global project on artificial photosynthesis
journal, January 2013

Semiconducting black phosphorus: synthesis, transport properties and electronic applications
journal, January 2015

Highly Efficient Photocatalytic Water Splitting over Edge-Modified Phosphorene Nanoribbons
journal, October 2017

Advances in surface passivation and emitter optimization techniques of c-Si solar cells
journal, February 2014

Visible-Light-Responsive β-Rhombohedral Boron Photocatalysts
journal, April 2013

Photooxidation and quantum confinement effects in exfoliated black phosphorus
journal, May 2015

Counteracting Blueshift Optical Absorption and Maximizing Photon Harvest in Carbon Nitride Nanosheet Photocatalyst
journal, April 2017

Black phosphorus: A promising two dimensional visible and near-infrared-activated photocatalyst for hydrogen evolution
journal, November 2017

Facile bottom-up synthesis of partially oxidized black phosphorus nanosheets as metal-free photocatalyst for hydrogen evolution
journal, March 2018

Two-dimensional atomic crystals
journal, July 2005

Light-Induced Ambient Degradation of Few-Layer Black Phosphorus: Mechanism and Protection
journal, August 2016

Ambient Protection of Few-Layer Black Phosphorus via Sequestration of Reactive Oxygen Species
journal, May 2017

Black Phosphorus Revisited: A Missing Metal-Free Elemental Photocatalyst for Visible Light Hydrogen Evolution
journal, February 2017

In situfabrication of hierarchically porous g-C3N4 and understanding on its enhanced photocatalytic activity based on energy absorption
journal, November 2018

Future CO ₂ Emissions and Climate Change from Existing Energy Infrastructure
journal, September 2010

Efficient and Fast Synthesis of Few-Layer Black Phosphorus via Microwave-Assisted Liquid-Phase Exfoliation
journal, November 2017

A Benchmark Quantum Yield for Water Photoreduction on Amorphous Carbon Nitride
journal, August 2017

Two-dimensional layered composite photocatalysts
journal, January 2014

Production of few-layer phosphorene by liquid exfoliation of black phosphorus
journal, January 2014

Expressway to partially oxidized phosphorene
journal, April 2018

A metal-free polymeric photocatalyst for hydrogen production from water under visible light
journal, November 2008

Phosphorene: An Unexplored 2D Semiconductor with a High Hole Mobility
journal, March 2014

Interaction of Black Phosphorus with Oxygen and Water
journal, November 2016

Hydrogen Production by Molecular Photocatalysis
journal, October 2007

2D phosphorene as a water splitting photocatalyst: fundamentals to applications
journal, January 2016

Phosphorene as a Superior Gas Sensor: Selective Adsorption and Distinct I – V Response
journal, July 2014

TiO ₂ Photocatalysis: A Historical Overview and Future Prospects
journal, December 2005

Black phosphorus field-effect transistors
journal, March 2014

Nitrogen-Doped Graphene Oxide Quantum Dots as Photocatalysts for Overall Water-Splitting under Visible Light Illumination
journal, February 2014

Reduced recombination and low-resistive transport of electrons for photo-redox reactions in metal-free hybrid photocatalyst
journal, June 2018

Topological carbon nitride: localized photon absorption and delocalized charge carrier separation at intertwined photocatalyst interfaces
journal, January 2018

Light-Induced Ambient Degradation of Few-Layer Black Phosphorus: Mechanism and Protection
journal, August 2016

Two-Dimensional Material Nanophotonics
text, January 2018

Hydrogen Production by Molecular Photocatalysis
journal, December 2007

Phosphorene as a superior gas sensor: Selective adsorption and distinct I-V response
preprint, January 2014

Two Dimensional Atomic Crystals
text, January 2005

Black Phosphorus‐Based Semiconductor Heterojunctions for Photocatalytic Water Splitting
journal, January 2020

Microwave-assisted synthesis of black phosphorus quantum dots: efficient electrocatalyst for oxygen evolution reaction
journal, January 2019