Facet-Specific Photocatalytic Degradation of Organics by Heterogeneous Fenton Chemistry on Hematite Nanoparticles

Huang, Xiaopeng; Chen, Ying; Walter, Eric D.; Zong, Meirong; Wang, Yang; Zhang, Xin; Qafoku, Odeta; Wang, Zheming; Rosso, Kevin M.

doi:10.1021/acs.est.9b02946

Title: Facet-Specific Photocatalytic Degradation of Organics by Heterogeneous Fenton Chemistry on Hematite Nanoparticles

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Abstract

Hematite nanoparticles are abundant in the photic zone of aquatic environments, where they play a prominent role in photocatalytic transformations of bound organics. In this work, we examine the photocatalytic degradation of rhodamine B (RhB) by visible light using two different structurally well-defined hematite nanoparticle morphologies. In addition to detailed solids characterization and aqueous kinetics measurements, we also exploit species-selective scavengers in electron paramagnetic spectroscopy (EPR) to sequester specific reaction channels and thereby assess their impact. Photodegradation rates for nanoplates dominated by {001} facets and nanocubes dominated by {012} facets were 0.13 and 0.7 h^-1, respectively, and turn over frequencies for the active sites on {001} and {012} were 7.89 × 10^-3 and 3.07× 10^-3 s^-1, yielding apparent activation energies of 17.13 and 24.94 kcal/mol within the energetic span model. Facet-specific differences appear directly linked not with the simple aerial cation site density but instead with their extent of undercoordination. By establishing this linkage, the findings lay a foundation for predicting the photocatalytic degradation efficiency for the myriad of possible hematite nanoparticle morphologies, and more broadly help unveil key reactions at the interface that may govern photocatalytic organic transformations in natural and engineered aquatic environments.

Authors:

^[1];

^[1]; Zong, Meirong ^[1]; Wang, Yang ^[1]; Zhang, Xin ^[1]; Qafoku, Odeta ^[1];

^[1];

^[1]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Publication Date:: Fri Aug 09 00:00:00 EDT 2019

Research Org.:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

OSTI Identifier:: 1729871

Report Number(s):: PNNL-SA-146189
Journal ID: ISSN 0013-936X

Grant/Contract Number:: AC05-76RL01830

Resource Type:: Accepted Manuscript

Journal Name:: Environmental Science and Technology

Additional Journal Information:: Journal Volume: 53; Journal Issue: 17; Journal ID: ISSN 0013-936X

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; degradation; hydroxyls; iron; nanoparticles; hematite

Citation Formats


                    Huang, Xiaopeng, Chen, Ying, Walter, Eric D., Zong, Meirong, Wang, Yang, Zhang, Xin, Qafoku, Odeta, Wang, Zheming, and Rosso, Kevin M. Facet-Specific Photocatalytic Degradation of Organics by Heterogeneous Fenton Chemistry on Hematite Nanoparticles.  United States: N. p., 2019. 
Web.  doi:10.1021/acs.est.9b02946.

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                    Huang, Xiaopeng, Chen, Ying, Walter, Eric D., Zong, Meirong, Wang, Yang, Zhang, Xin, Qafoku, Odeta, Wang, Zheming, & Rosso, Kevin M. Facet-Specific Photocatalytic Degradation of Organics by Heterogeneous Fenton Chemistry on Hematite Nanoparticles.  United States.  https://doi.org/10.1021/acs.est.9b02946

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                    Huang, Xiaopeng, Chen, Ying, Walter, Eric D., Zong, Meirong, Wang, Yang, Zhang, Xin, Qafoku, Odeta, Wang, Zheming, and Rosso, Kevin M. Fri .  
"Facet-Specific Photocatalytic Degradation of Organics by Heterogeneous Fenton Chemistry on Hematite Nanoparticles".  United States.  https://doi.org/10.1021/acs.est.9b02946.  https://www.osti.gov/servlets/purl/1729871.

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@article{osti_1729871,

  title        = {Facet-Specific Photocatalytic Degradation of Organics by Heterogeneous Fenton Chemistry on Hematite Nanoparticles},

  author       = {Huang, Xiaopeng and Chen, Ying and Walter, Eric D. and Zong, Meirong and Wang, Yang and Zhang, Xin and Qafoku, Odeta and Wang, Zheming and Rosso, Kevin M.},

  abstractNote = {Hematite nanoparticles are abundant in the photic zone of aquatic environments, where they play a prominent role in photocatalytic transformations of bound organics. In this work, we examine the photocatalytic degradation of rhodamine B (RhB) by visible light using two different structurally well-defined hematite nanoparticle morphologies. In addition to detailed solids characterization and aqueous kinetics measurements, we also exploit species-selective scavengers in electron paramagnetic spectroscopy (EPR) to sequester specific reaction channels and thereby assess their impact. Photodegradation rates for nanoplates dominated by {001} facets and nanocubes dominated by {012} facets were 0.13 and 0.7 h-1, respectively, and turn over frequencies for the active sites on {001} and {012} were 7.89 × 10-3 and 3.07× 10-3 s-1, yielding apparent activation energies of 17.13 and 24.94 kcal/mol within the energetic span model. Facet-specific differences appear directly linked not with the simple aerial cation site density but instead with their extent of undercoordination. By establishing this linkage, the findings lay a foundation for predicting the photocatalytic degradation efficiency for the myriad of possible hematite nanoparticle morphologies, and more broadly help unveil key reactions at the interface that may govern photocatalytic organic transformations in natural and engineered aquatic environments.},

  doi          = {10.1021/acs.est.9b02946},

  journal      = {Environmental Science and Technology},

  number       = 17,

  volume       = 53,

  place        = {United States},

  year         = {Fri Aug 09 00:00:00 EDT 2019},

  month        = {Fri Aug 09 00:00:00 EDT 2019}

}

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