Development of TiO₂ mesocrystal reactive electrochemical membranes for rapid removal of organic pollutants from water

Abstract

The use of titanium oxide (TiO₂) in electrochemical systems has been intensively investigated for developing conductive and active electrodes. However, achieving an effective reaction using geometric and electronic structures remains a challenge. Herein, we report the in situ synthesis of TiO₂ mesocrystals within a flow-through titanium (Ti) plate using an electrochemical method. We developed an electrochemical reactive membrane (REM) for the rapid removal of organic pollutants from water. At a low current density (3 mA/cm²), the removal rate of p-nitrophenol through the TiO₂ mesocrystal–based REM was 95% within 20 min. The REM demonstrated a service lifetime of > 1900 h and an energy consumption of 30 kWh (kg⁻¹ chemical oxygen demand) for treating organic pollutants in water. The abundant nanochannels of TiO₂ mesocrystals can effectively regulate the hydroxy radical reaction pathway, promoting its interaction with organic compounds more compared with the anode. This greatly enhances the electrochemical oxidation of organic pollutants in aqueous solution.

Graphical abstract

Keywords

TiO₂ mesocrystals / Reactive electrochemical membrane / Electrochemical oxidation / Water treatment

Highlight

	● The TiO2 mesocrystal REM was fabricated by an electrochemical method.
	● The reduced TiO2 mesocrystals showed excellent conductivity and reactivity.
	● The formation of nanochannels improves the selectivity of ∙OH to pollutants.
	● TiO2 mesocrystal REM had the extended lifetime (1987.9 h) via nanochannels.

References

[1] Almassi S , Ren C X , Liu J Y , Chaplin B P . (2022). Electrocatalytic perchlorate reduction using an oxorhenium complex supported on a Ti₄O₇ reactive electrochemical membrane. Environmental Science & Technology, 56(5): 3267–3276

[2] Brillas E . (2021). Recent development of electrochemical advanced oxidation of herbicides. A review on its application to wastewater treatment and soil remediation. Journal of Cleaner Production, 290: 125841

[3] Cai J J , Zhou M H , Pan Y W , Du X D , Lu X Y . (2019). Extremely efficient electrochemical degradation of organic pollutants with co-generation of hydroxyl and sulfate radicals on Blue-TiO₂ nanotubes anode. Applied Catalysis B: Environmental, 257: 117902

[4] Cho K , Hoffmann M R . (2015). Bi_xTi_1–xO_z functionalized heterojunction anode with an enhanced reactive chlorine generation efficiency in dilute aqueous solutions. Chemistry of Materials, 27(6): 2224–2233

[5] Cölfen H , Antonietti M . (2005). Mesocrystals: inorganic superstructures made by highly parallel crystallization and controlled alignment. Angewandte Chemie International Edition, 44(35): 5576–5591

[6] Crossland E J W , Noel N , Sivaram V , Leijtens T , Alexander-Webber J A , Snaith H J . (2013). Mesoporous TiO₂ single crystals delivering enhanced mobility and optoelectronic device performance. Nature, 495(7440): 215–219

[7] Guo L , Jing Y , Chaplin B P . (2016). Development and characterization of ultrafiltration TiO₂ Magnéli phase reactive electrochemical membranes. Environmental Science & Technology, 50(3): 1428–1436

[8] Hahn R , Schmidt-Stein F , Salonen J , Thiemann S , Song Y Y , Kunze J , Lehto V P , Schmuki P . (2009). Semimetallic TiO₂ nanotubes. Angewandte Chemie International Edition, 48(39): 7236–7239

[9] He Q , Sun Z G , Shi X W , Wu W W , Cheng J P , Zhuo R F , Zhang Z Y , Wang J . (2021). Electrochemical performance enhancement of nitrogen-doped TiO₂ for lithium-ion batteries investigated by a film electrode model. Energy &Fuels, 35(3): 2717–2726

[10] He Y P , Huang W M , Chen R L , Zhang W L , Lin H B , Li H D . (2015). Anodic oxidation of aspirin on PbO₂, BDD and porous Ti/BDD electrodes: mechanism, kinetics and utilization rate. Separation and Purification Technology, 156: 124–131

[11] Hong Z S , Wei M D , Lan T B , Cao G Z . (2012). Self-assembled nanoporous rutile TiO₂ mesocrystals with tunable morphologies for high rate lithium-ion batteries. Nano Energy, 1(3): 466–471

[12] Hu W P , Wen Z L , Yu X , Qian P S , Lian W T , Li X C , Shang Y B , Wu X J , Chen T , Lu Y L . et al. (2021). In situ surface fluorination of TiO₂ nanocrystals reinforces interface binding of perovskite layer for highly efficient solar cells with dramatically enhanced ultraviolet-light stability. Advanced Science, 8(10): 2004662

[13] Hu Z , Li K N , Wu X F , Wang N , Li X F , Li Q , Li L , Lv K L . (2019). Dramatic promotion of visible-light photoreactivity of TiO₂ hollow microspheres towards NO oxidation by introduction of oxygen vacancy. Applied Catalysis B: Environmental, 256: 117860

[14] Huang J F , Lei Y , Luo T , Liu J M . (2020). Photocatalytic H₂ production from water by metal-free dye-sensitized TiO₂ semiconductors: the role and development process of organic sensitizers. ChemSusChem, 13(22): 5863–5895

[15] Jenewein C , Schupp S M , Ni B , Schmidt-Mende L , Cölfen H . (2022). Tuning the electronic properties of mesocrystals. Small Science, 2(8): 2200014

[16] Joshi R K , Carbone P , Wang F C , Kravets V G , Su Y , Grigorieva I V , Wu H A , Geim A K , Nair R R . (2014). Precise and ultrafast molecular sieving through graphene oxide membranes. Science, 343(6172): 752–754

[17] Kesselman J M , Weres O , Lewis N S , Hoffmann M R . (1997). Electrochemical production of hydroxyl radical at polycrystalline Nb-doped TiO₂ electrodes and estimation of the partitioning between hydroxyl radical and direct hole oxidation pathways. The Journal of Physical Chemistry B, 101(14): 2637–2643

[18] Lee S , Lee G H , Kim J C , Kim D W . (2018). Magnéli-phase Ti₄O₇ nanosphere electrocatalyst support for carbon-free oxygen electrodes in lithium–oxygen batteries. ACS Catalysis, 8(3): 2601–2610

[19] Li W , Xiao R L , Lin H , Yang K , Li W , He K C , Yang L H , Pu M J , Li M Y , Lv S H . (2022a). Electro-activation of peroxy-monosulfate by a graphene oxide/iron oxide nanoparticle-doped Ti₄O₇ ceramic membrane: mechanism of singlet oxygen generation in the removal of 1,4-dioxane. Journal of Hazardous Materials, 424: 127342

[20] Li W , Xiao R L , Xu J L , Lin H , Yang K , Li W , He K C , Tang L X , Chen J , Wu Y P . et al. (2022b). Interface engineering strategy of a Ti₄O₇ ceramic membrane via graphene oxide nanoparticles toward efficient electrooxidation of 1,4-dioxane. Water Research, 216: 118287

[21] Li Y , Qing Y C , Li W , Zong M , Luo F . (2021). Novel Magnéli Ti₄O₇/Ni/poly(vinylidene fluoride) hybrids for high-performance electromagnetic wave absorption. Advanced Composites and Hybrid Materials, 4(4): 1027–1038

[22] Li Y H , Wu X F , Duan Y Y , Huang Z A , Fan J J , Carabineiro S A C , Lv K L . (2022c). Oxygen vacancies-induced photoreactivity enhancement of TiO₂ mesocrystals towards acetone oxidation. Applied Surface Science, 594: 153519

[23] Li Z L , Li Z Q , Zuo C L , Fang X S . (2022d). Application of nanostructured TiO₂ in UV photodetectors: a review. Advanced Materials, 34(28): 2109083

[24] Liu C , Lu H B , Zhang J N , Gao J Z , Zhu G Q , Yang Z B , Yin F , Wang C L . (2018). Crystal facet-dependent p-type and n-type sensing responses of TiO₂ nanocrystals. Sensors and Actuators B: Chemical, 263: 557–567

[25] Maneeratana V , Portehault D , Chaste J , Mailly D , Antonietti M , Sanchez C . (2014). Original electrospun core-shell nanostructured Magnéli titanium oxide fibers and their electrical properties. Advanced Materials, 26(17): 2654–2658

[26] Musial J , Mlynarczyk D T , Stanisz B J . (2023). Photocatalytic degradation of sulfamethoxazole using TiO₂-based materials – perspectives for the development of a sustainable water treatment technology. Science of the Total Environment, 856: 159122

[27] Nair R R , Wu H A , Jayaram P N , Grigorieva I V , Geim A K . (2012). Unimpeded permeation of water through helium-leak–tight graphene-based membranes. Science, 335(6067): 442–444

[28] Pan J , Liu G , Lu G Q , Cheng H M . (2011). On the true photo-reactivity order of {001}, {010}, and {101} facets of anatase TiO₂ crystals. Angewandte Chemie International Edition, 50(9): 2133–2137

[29] Qian Q J , Xiao P Z , Du T H , Xu D M , Guo C S , Guan Y , Yan M X , Wang F H , Zhang Y H , Li Y . (2024). Electrochemical oxidation of reverse osmosis concentrates from landfill leachate treatment using Ti₄O₇-nanotube reactive electrochemical membrane. Water, 16(24): 3579

[30] Qian X B , Xu L , Zhu Y Q , Yu H Y , Niu J F . (2021). Removal of aqueous triclosan using TiO₂ nanotube arrays reactive membrane by sequential adsorption and electrochemical degradation. Chemical Engineering Journal, 420: 127615

[31] Qu J S , Wang Y S , Mu X L , Hu J C , Zeng B , Lu Y , Sui M , Li R G , Li C . (2022). Determination of crystallographic orientation and exposed facets of titanium oxide nanocrystals. Advanced Materials, 34(37): 2203320

[32] Ran X X , Tao J M , Chen Z Y , Yan Z R , Yang Y M , Li J X , Lin Y B , Huang Z G . (2020). Surface heterostructure induced by TiO₂ modification in Li-rich cathode materials for enhanced electrochemical performances. Electrochimica Acta, 353: 135959

[33] Reier T , Oezaslan M , Strasser P . (2012). Electrocatalytic oxygen evolution reaction (OER) on Ru, Ir, and Pt catalysts: a comparative study of nanoparticles and bulk materials. ACS Catalysis, 2(8): 1765–1772

[34] Ren L H , Li Y , Guo Y , Yang K , Yi Q Y , Wang X Y , Wu Z C , Wang Z W . (2024). Electrochemical oxidation of reverse osmosis concentrate using a pilot-scale reactive electrochemical membrane filtration system: performance and mechanisms. Journal of Hazardous Materials, 465: 133315

[35] Sarkar A , Khan G G . (2019). The formation and detection techniques of oxygen vacancies in titanium oxide-based nanostructures. Nanoscale, 11(8): 3414–3444

[36] Su Z X , Li H . (2022). (NH₄)₃TiOF₅ mesocrystals grown by electric-field-assisted oriented-particle aggregation and their conversion to a TiO₂ superstructure. Electrochemistry Communications, 136: 107223

[37] Takimoto D , Toda Y , Tominaka S , Mochizuki D , Sugimoto W . (2019). Conductive nanosized Magnéli-phase Ti₄O₇ with a core@shell structure. Inorganic Chemistry, 58(10): 7062–7068

[38] Tian J , Zhao Z H , Kumar A , Boughton R I , Liu H . (2014). Recent progress in design, synthesis, and applications of one-dimensional TiO₂ nanostructured surface heterostructures: a review. Chemical Society Reviews, 43(20): 6920–6937

[39] Wang H J , Li Z Y , Zhang F Y , Wang Y X , Zhang X , Wang J B , He X W . (2021). Comparison of Ti/Ti₄O₇, Ti/Ti₄O₇-PbO₂-Ce, and Ti/Ti₄O₇ nanotube array anodes for electro-oxidation of p-nitrophenol and real wastewater. Separation and Purification Technology, 266: 118600

[40] Wang K X , Zhao K , Qin X , Chen S , Yu H T , Quan X . (2022). Treatment of organic wastewater by a synergic electrocatalysis process with Ti³⁺ self-doped TiO₂ nanotube arrays electrode as both cathode and anode. Journal of Hazardous Materials, 424: 127747

[41] Wei H , Rodriguez E F , Best A S , Hollenkamp A F , Chen D H , Caruso R A . (2017). Chemical bonding and physical trapping of sulfur in mesoporous Magnéli Ti₄O₇ microspheres for high-performance Li-S battery. Advanced Energy Materials, 7(4): 1601616

[42] Wu H L , Yang Y K , Ou Y , Lu B , Li J , Yuan W T , Wang Y , Zhang Z . (2018). Early stage growth of rutile titania mesocrystals. Crystal Growth & Design, 18(8): 4209–4214

[43] Wu J X , Liu H W , Tang A W , Zhang W F , Sheu H S , Lee J F , Liao Y F , Huang S P , Wei M D , Wu N L . (2022). Unexpected reversible crystalline/amorphous (de)lithiation transformations enabling fast (dis)charge of high-capacity anatase mesocrystal anode. Nano Energy, 102: 107715

[44] Wu Z X , Yang P F , Li Q C , Xiao W P , Li Z J , Xu G R , Liu F S , Jia B H , Ma T Y , Feng S H . et al. (2023). Microwave synthesis of Pt clusters on black TiO₂ with abundant oxygen vacancies for efficient acidic electrocatalytic hydrogen evolution. Angewandte Chemie International Edition, 62(14): e202300406

[45] Xu P L , Ding C C , Li Z M , Yu R T , Cui H R , Gao S W . (2023). Photocatalytic degradation of air pollutant by modified nano titanium oxide (TiO₂) in a fluidized bed photoreactor: optimizing and kinetic modeling. Chemosphere, 319: 137995

[46] Yang Y , Hoffmann M R . (2016). Synthesis and stabilization of blue-black TiO₂ nanotube arrays for electrochemical oxidant generation and wastewater treatment. Environmental Science & Technology, 50(21): 11888–11894

[47] Yang Y , Kao L C , Liu Y Y , Sun K , Yu H T , Guo J H , Liou S Y H , Hoffmann M R . (2018). Cobalt-doped black TiO₂ nanotube array as a stable anode for oxygen evolution and electrochemical wastewater treatment. ACS Catalysis, 8(5): 4278–4287

[48] Ye J F , Liu W , Cai J G , Chen S , Zhao X W , Zhou H H , Qi L M . (2011). Nanoporous anatase TiO₂ mesocrystals: additive-free synthesis, remarkable crystalline-phase stability, and improved lithium insertion behavior. Journal of the American Chemical Society, 133(4): 933–940

[49] You S J , Liu B , Gao Y F , Wang Y , Tang C Y , Huang Y B , Ren N Q . (2016). Monolithic porous Magnéli-phase Ti₄O₇ for electro-oxidation treatment of industrial wastewater. Electrochimica Acta, 214: 326–335

[50] Yu J F , Yu H J , Wang C H , Ma J Y , Wang J B . (2023). Preparation of Ti₄O₇ reactive electrochemical membrane for electrochemical oxidation of coking wastewater. Sustainability, 15(21): 15488

[51] Yuan Q B , Qu S Y , Li R , Huo Z Y , Gao Y , Luo Y . (2023). Degradation of antibiotics by electrochemical advanced oxidation processes (EAOPs): performance, mechanisms, and perspectives. Science of the Total Environment, 856: 159092

[52] Zaky A M , Chaplin B P . (2013). Porous substoichiometric TiO₂ anodes as reactive electrochemical membranes for water treatment. Environmental Science & Technology, 47(12): 6554–6563

[53] Žerjav G , Say Z , Zavašnik J , Finasni M , Langhammer C , Pintar A . (2023). Photo, thermal and photothermal activity of TiO₂ supported Pt catalysts for plasmon-driven environmental applications. Journal of Environmental Chemical Engineering, 11(3): 110209

[54] Zhang M M , Lu A J , Li H , Li M , Wang J L , Wang C R . (2023). Defective TiO₂-supported dual-Schottky heterostructure boosts fast reaction kinetics for high performance lithium-ion storage. ACS Applied Energy Materials, 6(3): 1781–1798

[55] Zhang P, Tachikawa T, Bian Z F, Majima T (2015). Selective photoredox activity on specific facet-dominated TiO₂ mesocrystal superstructures incubated with directed nanocrystals. Applied Catalysis B: Environmental, 176–177: 678–686

[56] Zhang W , He H L , Li H Z , Duan L L , Zu L H , Zhai Y P , Li W , Wang L Z , Fu H G , Zhao D Y . (2021). Visible-light responsive TiO₂-based materials for efficient solar energy utilization. Advanced Energy Materials, 11(15): 2003303

[57] Zhao Z Y , Zhang J N , Yao J , You S J . (2022). Electrochemical removal of 4-chlorophenol in water using a porous Magnéli-phase (Ti₄O₇) electrode. Environmental Research, 210: 113004

[58] Zhou S Y , Jiang L B , Wang H , Yang J J , Yuan X Z , Wang H , Liang J , Li X D , Li H , Bu Y Q . (2023). Oxygen vacancies modified TiO₂/O-terminated Ti₃C₂ composites: unravelling the dual effects between oxygen vacancy and high-work-function titanium carbide. Advanced Functional Materials, 33(41): 2307702

[59] Zhu B E , Xu Z , Wang C L , Gao Y . (2016). Shape evolution of metal nanoparticles in water vapor environment. Nano Letters, 16(4): 2628–2632

Rights & permissions

Higher Education Press 2027