Facet‐dependent Heterogeneous Fenton Reaction Mechanisms on Hematite Nanoparticles for (Photo)catalytic Degradation of Organic Dyes

Chen, Ping; Song, Duo; Liu, Tianying; Chen, Ying; Zhou, Yadong; Prange, Micah P.; Chen, Tianhu; Wang, David Z.; Zhao, Yatong; Wang, Xiang; Li, Xiaoxu; Wang, Dunwei; Zhu, Zihua; Wang, Zheming; Rosso, Kevin M.; Zhang, Xin

doi:10.1002/advs.202508058

Facet‐dependent Heterogeneous Fenton Reaction Mechanisms on Hematite Nanoparticles for (Photo)catalytic Degradation of Organic Dyes

Journal Article · Sat Sep 06 00:00:00 EDT 2025 · Advanced Science

DOI:https://doi.org/10.1002/advs.202508058· OSTI ID:3005015

Chen, Ping ^[1]; Song, Duo ^[2]; Liu, Tianying ^[3]; ^[2]; Zhou, Yadong ^[4]; ^[2]; Chen, Tianhu ^[5]; Wang, David Z. ^[3]; Zhao, Yatong ^[2]; Wang, Xiang ^[2]; Li, Xiaoxu ^[2]; Wang, Dunwei ^[3]; ^[4]; ^[2]; ^[2]; ^[2]

Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Hefei Univ. of Technology (China)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Boston College, Chestnut Hill, MA (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)
Hefei Univ. of Technology (China)

Although heterogeneous photo‐Fenton reactions on nanoparticulate iron oxides effectively degrade organic pollutants, the underlying surface mechanisms remain debated. Here, we demonstrate how these pathways are modulated by specific hematite crystal facets. To investigate the influence of particle surface structure, methylene blue (MB) adsorption and photodegradation kinetics are examined using facet‐engineered hematite nanoparticles with distinct exposed facets. The results reveal that MB photodegradation strongly depends on both pH and facet orientation. When normalized by surface area, (116) facet shows higher photodegradation activity than those with (104) or (001) facets. This enhanced activity is attributed to favorable electronic structure and surface characteristics, including a smaller optical bandgap, faster charge transfer, and superior H₂O₂ decomposition. In contrast, the photodegradation capacity follows (104) 〉 (116) 〉 (001), primarily due to the higher density of surface‐active sites on the (104) facet. These sites promote coupled MB adsorption and degradation, enabling removal of a greater overall quantity of MB. Additionally, under high pH conditions, hematite can degrade MB in the dark, with capacities following (001) ≫ (116) 〉 (104). These findings underscore the critical catalytic role of specific hematite surfaces and advance the understanding of facet‐dependent photoinduced redox chemistry at mineral–water interfaces.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: National Science Foundation of China (NSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC02-05CH11231; AC05-76RL01830

OSTI ID:: 3005015

Report Number(s):: PNNL-SA--211231

Journal Information:: Advanced Science, Journal Name: Advanced Science Journal Issue: 43 Vol. 12; ISSN 2198-3844

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (62)

A Hierarchical Z-Scheme α-Fe ₂ O ₃ /g-C ₃ N ₄ Hybrid for Enhanced Photocatalytic CO ₂ Reduction Jiang, Zhifeng; Wan, Weiming; Li, Huaming Advanced Materials, Vol. 30, Issue 10 https://doi.org/10.1002/adma.201706108	journal	January 2018
Surface, Bulk, and Interface: Rational Design of Hematite Architecture toward Efficient Photo-Electrochemical Water Splitting Li, Chengcheng; Luo, Zhibin; Wang, Tuo Advanced Materials, Vol. 30, Issue 30 https://doi.org/10.1002/adma.201707502	journal	May 2018
Surface Modification of 2D Photocatalysts for Solar Energy Conversion Feng, Chengyang; Wu, Zhi‐Peng; Huang, Kuo‐Wei Advanced Materials, Vol. 34, Issue 23 https://doi.org/10.1002/adma.202200180	journal	April 2022
Facet-Mediated Photodegradation of Organic Dye over Hematite Architectures by Visible Light Zhou, Xuemei; Lan, Jinyao; Liu, Gang Angewandte Chemie International Edition, Vol. 51, Issue 1 https://doi.org/10.1002/anie.201105028	journal	November 2011
Spot the Difference: Engineered and Natural Nanoparticles in the Environment—Release, Behavior, and Fate Wagner, Stephan; Gondikas, Andreas; Neubauer, Elisabeth Angewandte Chemie International Edition, Vol. 53, Issue 46 https://doi.org/10.1002/anie.201405050	journal	October 2014
Origin of Tunable Photocatalytic Selectivity of Well-Defined α-Fe ₂ O ₃ Nanocrystals Zhou, Xuemei; Xu, Quanlong; Lei, Wanying Small, Vol. 10, Issue 4 https://doi.org/10.1002/smll.201301870	journal	September 2013
Quantitative Measurement of Superoxide Generation Using the Spin Trap 5-(Diethoxyphosphoryl)-5-methyl- 1-pyrroline-N-oxide Roubaud, Valerie; Sankarapandi, Sornampillai; Kuppusamy, Periannan Analytical Biochemistry, Vol. 247, Issue 2 https://doi.org/10.1006/abio.1997.2067	journal	May 1997
Anisotropic photocatalytic properties of hematite Eggleston, Carrick M.; Shankle, Angela J. A.; Moyer, Amanda J. Aquatic Sciences, Vol. 71, Issue 2 https://doi.org/10.1007/s00027-009-9191-5	journal	May 2009
Facile fabrication of Zn-doped SnO2 nanoparticles for enhanced photocatalytic dye degradation performance under visible light exposure Ali Baig, Ameer Baig; Rathinam, Vadamalar; Ramya, Velukumar Advanced Composites and Hybrid Materials, Vol. 4, Issue 1 https://doi.org/10.1007/s42114-020-00195-9	journal	January 2021
Synthesis of graphitic carbon nitride/zinc oxide (g-C3N4/ZnO) hybrid nanostructures and investigation of the effect of ZnO on the photodegradation activity of g-C3N4 against the brilliant cresyl blue (BCB) dye under visible light irradiation Meena, Parmeshwar Lal; Poswal, Krishna; Surela, Ajay Kumar Advanced Composites and Hybrid Materials, Vol. 6, Issue 1 https://doi.org/10.1007/s42114-022-00577-1	journal	December 2022
A review of classic Fenton’s peroxidation as an advanced oxidation technique Neyens, E.; Baeyens, J. Journal of Hazardous Materials, Vol. 98, Issue 1-3 https://doi.org/10.1016/S0304-3894(02)00282-0	journal	March 2003
A new catalyst material based on niobia/iron oxide composite on the oxidation of organic contaminants in water via heterogeneous Fenton mechanisms Oliveira, L. C. A.; Gonçalves, M.; Guerreiro, M. C. Applied Catalysis A: General, Vol. 316, Issue 1 https://doi.org/10.1016/j.apcata.2006.09.027	journal	January 2007
Degradation of Acid Blue 74 using Fe-ZSM5 zeolite as a heterogeneous photo-Fenton catalyst Kasiri, M. B.; Aleboyeh, H.; Aleboyeh, A. Applied Catalysis B: Environmental, Vol. 84, Issue 1-2 https://doi.org/10.1016/j.apcatb.2008.02.024	journal	October 2008
Unfolding the action mode of light and homogeneous vs. heterogeneous photo-Fenton in bacteria disinfection and concurrent elimination of micropollutants in urban wastewater, mediated by iron oxides in Raceway Pond Reactors de la Obra Jiménez, Irene; Giannakis, Stefanos; Grandjean, Dominique Applied Catalysis B: Environmental, Vol. 263 https://doi.org/10.1016/j.apcatb.2019.118158	journal	April 2020
Facile synthesis of mesoporous anatase/rutile/hematite triple heterojunctions for superior heterogeneous photo-Fenton catalysis Zhang, Xiangcheng; Zhang, Yi; Yu, Zhikai Applied Catalysis B: Environmental, Vol. 263 https://doi.org/10.1016/j.apcatb.2019.118335	journal	April 2020
Enhanced charge transfer with tuning surface state in hematite photoanode integrated by niobium and zirconium co-doping for efficient photoelectrochemical water splitting Dhandole, Love Kumar; Koh, Tae Sik; Anushkkaran, Periyasamy Applied Catalysis B: Environmental, Vol. 315 https://doi.org/10.1016/j.apcatb.2022.121538	journal	October 2022
Facet-dependent photo-degradation of nitro polycyclic aromatic hydrocarbons on hematite under visible light: Participation of environmentally persistent free radicals and reactive oxygen/nitrogen species Ni, Zheng; Zhang, Chi; Ma, Haonan Applied Catalysis B: Environmental, Vol. 318 https://doi.org/10.1016/j.apcatb.2022.121816	journal	December 2022
Sunlight-hematite promoted denitrification by Pseudomonas aeruginosa: A little-known form of nitrogen-cycling enhancement Wang, Qijun; Ren, Guiping; Zhao, Xu Applied Geochemistry, Vol. 146 https://doi.org/10.1016/j.apgeochem.2022.105464	journal	November 2022
Adsorption of copper to different biogenic oyster shell structures Wu, Qiong; Chen, Jie; Clark, Malcolm Applied Surface Science, Vol. 311 https://doi.org/10.1016/j.apsusc.2014.05.054	journal	August 2014
A review on photocatalysis for air treatment: From catalyst development to reactor design Boyjoo, Yash; Sun, Hongqi; Liu, Jian Chemical Engineering Journal, Vol. 310 https://doi.org/10.1016/j.cej.2016.06.090	journal	February 2017
Carbon-integrated semiconductor photocatalysts for removal of volatile organic compounds in indoor environments Ahmad, Adnan; Ali, Mumtaz; Al-Sehemi, Abdullah G. Chemical Engineering Journal, Vol. 452 https://doi.org/10.1016/j.cej.2022.139436	journal	January 2023
Machine learning assisted phase and size-controlled synthesis of iron oxide particles Liu, Juejing; Zhang, Zimeng; Li, Xiaoxu Chemical Engineering Journal, Vol. 473 https://doi.org/10.1016/j.cej.2023.145216	journal	October 2023
Photocatalytic degradation of amoxicillin, ampicillin and cloxacillin antibiotics in aqueous solution using UV/TiO2 and UV/H2O2/TiO2 photocatalysis Elmolla, Emad S.; Chaudhuri, Malay Desalination, Vol. 252, Issue 1-3 https://doi.org/10.1016/j.desal.2009.11.003	journal	March 2010
High adsorption of methylene blue by salicylic acid–methanol modified steel converter slag and evaluation of its mechanism Cheng, Min; Zeng, Guangming; Huang, Danlian Journal of Colloid and Interface Science, Vol. 515 https://doi.org/10.1016/j.jcis.2018.01.008	journal	April 2018
Effects of iron (hydr)oxides on the degradation of diethyl phthalate ester in heterogeneous (photo)-Fenton reactions Shuai, Wenjuan; Gu, Cheng; Fang, Guodong Journal of Environmental Sciences, Vol. 80 https://doi.org/10.1016/j.jes.2018.06.015	journal	June 2019
Kinetic study on photocatalytic degradation of C.I. Acid Yellow 23 by ZnO photocatalyst Behnajady, M.; Modirshahla, N.; Hamzavi, R. Journal of Hazardous Materials, Vol. 133, Issue 1-3 https://doi.org/10.1016/j.jhazmat.2005.10.022	journal	May 2006
Synthesis and characterization of hematite pigment obtained from a steel waste industry Prim, S. R.; Folgueras, M. V.; de Lima, M. A. Journal of Hazardous Materials, Vol. 192, Issue 3 https://doi.org/10.1016/j.jhazmat.2011.06.034	journal	September 2011
Review of iron-free Fenton-like systems for activating H2O2 in advanced oxidation processes Bokare, Alok D.; Choi, Wonyong Journal of Hazardous Materials, Vol. 275 https://doi.org/10.1016/j.jhazmat.2014.04.054	journal	June 2014
Adsorption and photodegradation of reactive red 120 with nickel-iron-layered double hydroxide/biochar composites Luo, Yidan; Wang, Yonghu; Hua, Feng Journal of Hazardous Materials, Vol. 443 https://doi.org/10.1016/j.jhazmat.2022.130300	journal	February 2023
Cubic shaped hematite (α-Fe2O3) micro-structures composed of stacked nanosheets for rapid ethanol sensor application Umar, Ahmad; Ibrahim, Ahmed A.; Kumar, Rajesh Sensors and Actuators B: Chemical, Vol. 326 https://doi.org/10.1016/j.snb.2020.128851	journal	January 2021
Oxygen vacancy engineering and superior sensing properties of hematite prepared via a one-step treatment Ma, Min; Peng, Lin; Li, Jiayi Sensors and Actuators B: Chemical, Vol. 339 https://doi.org/10.1016/j.snb.2021.129907	journal	July 2021
Occurrence of unknown reactive species in UV/H2O2 system leading to false interpretation of hydroxyl radical probe reactions Kim, Min Sik; Lee, Changha; Kim, Jae-Hong Water Research, Vol. 201 https://doi.org/10.1016/j.watres.2021.117338	journal	August 2021
Oxide– and Silicate–Water Interfaces and Their Roles in Technology and the Environment Bañuelos, José Leobardo; Borguet, Eric; Brown, Gordon E. Chemical Reviews, Vol. 123, Issue 10 https://doi.org/10.1021/acs.chemrev.2c00130	journal	May 2023
Facet-Dependent Photodegradation of Methylene Blue by Hematite Nanoplates in Visible Light Zong, Meirong; Song, Duo; Zhang, Xin Environmental Science & Technology, Vol. 55, Issue 1 https://doi.org/10.1021/acs.est.0c05592	journal	December 2020
Sunlight-Driven Production of Reactive Oxygen Species from Natural Iron Minerals: Quantum Yield and Wavelength Dependence Zheng, Xiaoshan; Wu, Binbin; Zhou, Chong Environmental Science & Technology, Vol. 57, Issue 2 https://doi.org/10.1021/acs.est.2c06942	journal	December 2022
Photolysis of Dissolved Organic Matter over Hematite Nanoplatelets Huang, Xiaopeng; Song, Duo; Zhao, Qian Environmental Science & Technology, Vol. 58, Issue 6 https://doi.org/10.1021/acs.est.3c08752	journal	January 2024
Overlooked Role of Photogenerated Holes in Persistent Free Radical Formation on Hematite Yi, Peng; Chen, Quan; Dong, Jihong Environmental Science & Technology, Vol. 59, Issue 11 https://doi.org/10.1021/acs.est.5c01376	journal	March 2025
Facet-Specific Photocatalytic Degradation of Organics by Heterogeneous Fenton Chemistry on Hematite Nanoparticles Huang, Xiaopeng; Chen, Ying; Walter, Eric Environmental Science & Technology, Vol. 53, Issue 17 https://doi.org/10.1021/acs.est.9b02946	journal	August 2019
Synthesis of 2D Hexagonal Hematite Nanosheets and the Crystal Growth Mechanism Zong, Meirong; Zhang, Xin; Wang, Yining Inorganic Chemistry, Vol. 58, Issue 24 https://doi.org/10.1021/acs.inorgchem.9b02883	journal	November 2019
Photocatalysis: From Fundamental Principles to Materials and Applications Yang, Xiaogang; Wang, Dunwei ACS Applied Energy Materials, Vol. 1, Issue 12 https://doi.org/10.1021/acsaem.8b01345	journal	October 2018
Nanostructure-Preserved Hematite Thin Film for Efficient Solar Water Splitting Kim, Jae Young; Youn, Duck Hyun; Kim, Ju Hun ACS Applied Materials & Interfaces, Vol. 7, Issue 25 https://doi.org/10.1021/acsami.5b03409	journal	June 2015
Facet-Dependent Kinetics and Energetics of Hematite for Solar Water Oxidation Reactions Li, Wei; Yang, Ke R.; Yao, Xiahui ACS Applied Materials & Interfaces, Vol. 11, Issue 6 https://doi.org/10.1021/acsami.8b05190	journal	May 2018
Mechanism of the ferric ion catalyzed decomposition of hydrogen peroxide. Effect of organic substrates Walling, Cheves.; Goosen, Andre. Journal of the American Chemical Society, Vol. 95, Issue 9 https://doi.org/10.1021/ja00790a042	journal	May 1973
Electronic Structure and Reactivity of Low-Spin Fe(III)−Hydroperoxo Complexes: Comparison to Activated Bleomycin Lehnert, Nicolai; Neese, Frank; Ho, Raymond Y. N. Journal of the American Chemical Society, Vol. 124, Issue 36 https://doi.org/10.1021/ja012621d	journal	August 2002
Mechanism of H ₂ O ₂ Decomposition on Transition Metal Oxide Surfaces Lousada, Cláudio M.; Johansson, Adam Johannes; Brinck, Tore The Journal of Physical Chemistry C, Vol. 116, Issue 17 https://doi.org/10.1021/jp300255h	journal	April 2012
Plasmon-induced photonic and energy-transfer enhancement of solar water splitting by a hematite nanorod array Li, Jiangtian; Cushing, Scott K.; Zheng, Peng Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3651	journal	October 2013
Probing the photoelectrochemical properties of hematite (α-Fe ₂ O ₃ ) electrodes using hydrogen peroxide as a hole scavenger Dotan, Hen; Sivula, Kevin; Grätzel, Michael Energy Environ. Sci., Vol. 4, Issue 3 https://doi.org/10.1039/C0EE00570C	journal	January 2011
Heterogeneous photo-Fenton reaction on hematite (α-Fe ₂ O ₃ ){104}, {113} and {001} surface facets Chan, J. Y. T.; Ang, S. Y.; Ye, E. Y. Physical Chemistry Chemical Physics, Vol. 17, Issue 38 https://doi.org/10.1039/C5CP03332B	journal	January 2015
Natural inorganic nanoparticles – formation, fate, and toxicity in the environment Sharma, Virender K.; Filip, Jan; Zboril, Radek Chemical Society Reviews, Vol. 44, Issue 23 https://doi.org/10.1039/C5CS00236B	journal	January 2015
Hematite heterostructures for photoelectrochemical water splitting: rational materials design and charge carrier dynamics Shen, Shaohua; Lindley, Sarah A.; Chen, Xiangyan Energy & Environmental Science, Vol. 9, Issue 9 https://doi.org/10.1039/C6EE01845A	journal	January 2016
Facet-dependent contaminant removal properties of hematite nanocrystals and their environmental implications Huang, Xiaopeng; Hou, Xiaojing; Zhang, Xin Environmental Science: Nano, Vol. 5, Issue 8 https://doi.org/10.1039/C8EN00548F	journal	January 2018
Photocatalyzed electron exchange between organic chromophores and hematite nanoparticles and the role of solid-state charge transport Boamah, Mavis D.; Huang, Xiaopeng; Joly, Alan Environmental Science: Nano, Vol. 9, Issue 11 https://doi.org/10.1039/D2EN00567K	journal	January 2022
Semiconductor-mediated photodegradation of pollutants under visible-light irradiation Chen, Chuncheng; Ma, Wanhong; Zhao, Jincai Chemical Society Reviews, Vol. 39, Issue 11 https://doi.org/10.1039/b921692h	journal	January 2010
DEPMPO: an efficient tool for the coupled ESR-spin trapping of alkylperoxyl radicals in water Karoui, Hakim; Chalier, Florence; Finet, Jean-Pierre Organic & Biomolecular Chemistry, Vol. 9, Issue 7 https://doi.org/10.1039/c0ob00876a	journal	January 2011
Surface potentials of (001), (012), (113) hematite (α-Fe2O3) crystal faces in aqueous solution Chatman, Shawn; Zarzycki, Piotr; Rosso, Kevin M. Physical Chemistry Chemical Physics, Vol. 15, Issue 33 https://doi.org/10.1039/c3cp52592a	journal	January 2013
Photoelectric conversion on Earth’s surface via widespread Fe- and Mn-mineral coatings Lu, Anhuai; Li, Yan; Ding, Hongrui Proceedings of the National Academy of Sciences, Vol. 116, Issue 20 https://doi.org/10.1073/pnas.1902473116	journal	April 2019
Particle-based hematite crystallization is invariant to initial particle morphology Wang, Yining; Xue, Sichuang; Lin, Qingyun Proceedings of the National Academy of Sciences, Vol. 119, Issue 11 https://doi.org/10.1073/pnas.2112679119	journal	March 2022
Nanominerals, Mineral Nanoparticles, and Earth Systems Hochella, M. F.; Lower, S. K.; Maurice, P. A. Science, Vol. 319, Issue 5870 https://doi.org/10.1126/science.1141134	journal	March 2008
Linked Reactivity at Mineral-Water Interfaces Through Bulk Crystal Conduction Yanina, S. V.; Rosso, K. M. Science, Vol. 320, Issue 5873 https://doi.org/10.1126/science.1154833	journal	March 2008
Natural, incidental, and engineered nanomaterials and their impacts on the Earth system Hochella, Michael F.; Mogk, David W.; Ranville, James Science, Vol. 363, Issue 6434 https://doi.org/10.1126/science.aau8299	journal	March 2019
Intermediate free radicals in the oxidation of wastewaters Bianchini, Roberto; Calucci, Lucia; Lubello, Claudio Research on Chemical Intermediates, Vol. 28, Issue 2-3 https://doi.org/10.1163/156856702320267154	journal	April 2002
Structure and Reactivity of Semiconducting Mineral Surfaces: Convergence of Molecular Modeling and Experiment Rosso, K. M. Reviews in Mineralogy and Geochemistry, Vol. 42, Issue 1 https://doi.org/10.2138/rmg.2001.42.7	journal	January 2001

Similar Records

Facet-Dependent Photodegradation of Methylene Blue by Hematite Nanoplates in Visible Light

Journal Article · Mon Jan 04 23:00:00 EST 2021 · Environmental Science & Technology · OSTI ID:1760311

Facet-Dependent Adsorption of Pb(II) on Hematite (001), (116), and (104) Surfaces

Journal Article · Sun Jun 01 20:00:00 EDT 2025 · Environmental Science and Technology · OSTI ID:3000471

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

Journal Article · Thu Aug 08 20:00:00 EDT 2019 · Environmental Science and Technology · OSTI ID:1729871

Related Subjects

(photo)catalytic degradation
facet-dependent reactivity
hematite
photo-fenton reactions
redox chemistry

Facet‐dependent Heterogeneous Fenton Reaction Mechanisms on Hematite Nanoparticles for (Photo)catalytic Degradation of Organic Dyes

Citation Formats

References (62)

Similar Records

Related Subjects