Formation of quasi-core-shell In2S3/anatase TiO2@metallic Ti3C2Tx hybrids with favorable charge transfer channels for excellent visible-light-photocatalytic performance

Abstract Semiconductor-based heterojunctions, widely applied in photocatalytic solar-to-chemical energy conversion, are advantageous for synergistically expediting photocatalytic reaction beyond individual the constituent components. Here we showed new quasi-core-shell In2S3/anatase TiO2@metallic Ti3C2Tx hybrids consisting of well-designed type-II heterojunction and non-noble metal-based Schottky junction with favorable charge transfer channels for efficient photocatalysis application. The mesoporous hybrids owned pleasurable visible-light absorption property and excellent capability in photogenerated exciton separation and carrier transport. Specifically, the hybridized photocatalyst with the additive Ti3C2Tx content of 16 mg (InTi-16) had excellent visible-light photocatalytic performance towards pollutant removal in water with a degradation rate of 0.04977 min−1, which was 3.2 and 6.2 folds higher than that of pure In2S3 and pure Ti3C2Tx, respectively. What’s more, the photocatalytic degradation ability of InTi-16 had surpassed that of many other types of In2S3-based photocatalyst including In2S3/carbon nanotube (CNT), In2S3/reduced graphene oxide (rGO), In2S3/MoS2, and In2S3/TiO2 hybrids. The promising photocatalytic performance was strongly depended on the separation and diffusion of photogenerated exciton and carrier via a multitude of charge transfer channels due to the formation of double heterostructure (type-II heterojunction and Schottky junction). It had originated from the synergistic effects among the visible-light absorption of In2S3, the upward band bending of TiO2 and the favorable electrical conductivity of Ti3C2Tx. Prolonger electron lifetime favored for the generation of more strongly oxidizing radical (e.g. ·O2-) at the in-plane of Ti3C2Tx, and thus enhanced photocatalytic degradation ability. This work demonstrates that the TiO2/Ti3C2Tx can be a potentially novel platform for constructing efficient photocatalysts both for wide-ranging applications and unraveling the transfer behavior of photo-excited electrons based on charge transfer channels.

[1]  M. Liu,et al.  Black phosphorus nanostructures: recent advances in hybridization, doping and functionalization. , 2017, Chemical Society reviews.

[2]  R. Grondelle,et al.  Quantum design of photosynthesis for bio-inspired solar-energy conversion , 2017, Nature.

[3]  Mohammad Khazaei,et al.  Electronic properties and applications of MXenes: a theoretical review , 2017, 1702.07442.

[4]  Hyochul Kim,et al.  Large Work Function Modulation of Monolayer MoS2 by Ambient Gases. , 2016, ACS nano.

[5]  L. An,et al.  Fabrication of layered Ti3C2 with an accordion-like structure as a potential cathode material for high performance lithium–sulfur batteries , 2015 .

[6]  R. Ruoff,et al.  Graphene, related two-dimensional crystals, and hybrid systems for energy conversion and storage , 2015, Science.

[7]  Zachary D. Hood,et al.  Titania Composites with 2 D Transition Metal Carbides as Photocatalysts for Hydrogen Production under Visible-Light Irradiation. , 2016, ChemSusChem.

[8]  Jixing Liu,et al.  A Unique Fe/Beta@TiO2 Core–Shell Catalyst by Small-Grain Molecular Sieve as the Core and TiO2 Nanosize Thin Film as the Shell for the Removal of NOx , 2017 .

[9]  Hong He,et al.  Photocatalytic Removal of NOx over Visible Light Responsive Oxygen-Deficient TiO2 , 2014 .

[10]  Hao Yu,et al.  Hybrids of Two-Dimensional Ti3C2 and TiO2 Exposing {001} Facets toward Enhanced Photocatalytic Activity. , 2016, ACS applied materials & interfaces.

[11]  K. Novoselov,et al.  2D materials and van der Waals heterostructures , 2016, Science.

[12]  Yury Gogotsi,et al.  Conductive two-dimensional titanium carbide ‘clay’ with high volumetric capacitance , 2014, Nature.

[13]  Ning Kang,et al.  Large-area high-quality 2D ultrathin Mo2C superconducting crystals. , 2015, Nature materials.

[14]  R. Banerjee,et al.  A covalent organic framework-cadmium sulfide hybrid as a prototype photocatalyst for visible-light-driven hydrogen production. , 2014, Chemistry.

[15]  Wei Chen,et al.  High performance supercapacitors based on three-dimensional ultralight flexible manganese oxide nanosheets/carbon foam composites , 2014 .

[16]  Byung Jin Cho,et al.  Determination of work function of graphene under a metal electrode and its role in contact resistance. , 2012, Nano letters.

[17]  Dongdong Wang,et al.  Fast electron transfer and enhanced visible light photocatalytic activity using multi-dimensional components of carbon quantum dots@3D daisy-like In2S3/single-wall carbon nanotubes , 2017 .

[18]  V. Presser,et al.  Two‐Dimensional Nanocrystals Produced by Exfoliation of Ti3AlC2 , 2011, Advanced materials.

[19]  Mustri Bano,et al.  Solar-assisted photocatalytic reduction of methyl orange azo dye over porous TiO2 nanostructures , 2016 .

[20]  M. Katsnelson,et al.  Many-body effects in graphene beyond the Dirac model with Coulomb interaction , 2015, 1506.00026.

[21]  Pooi See Lee,et al.  Recent progress in layered transition metal carbides and/or nitrides (MXenes) and their composites: synthesis and applications , 2017 .

[22]  Yury Gogotsi,et al.  Electromagnetic interference shielding with 2D transition metal carbides (MXenes) , 2016, Science.

[23]  Majid Beidaghi,et al.  Solving the Capacitive Paradox of 2D MXene using Electrochemical Quartz‐Crystal Admittance and In Situ Electronic Conductance Measurements , 2015 .

[24]  Hui Zhang,et al.  Anisotropic electronic conduction in stacked two-dimensional titanium carbide , 2015, Scientific Reports.

[25]  Liyi Shi,et al.  Design of meso-TiO2@MnO(x)-CeO(x)/CNTs with a core-shell structure as DeNO(x) catalysts: promotion of activity, stability and SO2-tolerance. , 2013, Nanoscale.

[26]  Hong Liu,et al.  In2S3 nanomaterial as a broadband spectrum photocatalyst to display significant activity , 2015 .

[27]  G. Zeng,et al.  Doping of graphitic carbon nitride for photocatalysis: A reveiw , 2017 .

[28]  Agatino Di Paola,et al.  Brookite, the Least Known TiO2 Photocatalyst , 2013 .

[29]  Fen Zhang,et al.  Controlled Synthesis of Semiconducting Metal Sulfide Nanowires , 2009 .

[30]  Qiang Fu,et al.  Catalysis with two-dimensional materials and their heterostructures. , 2016, Nature nanotechnology.

[31]  Sean C. Smith,et al.  The origin of low workfunctions in OH terminated MXenes. , 2017, Nanoscale.

[32]  Liyi Shi,et al.  Design of multi-shell Fe2O3@MnO(x)@CNTs for the selective catalytic reduction of NO with NH3: improvement of catalytic activity and SO2 tolerance. , 2016, Nanoscale.

[33]  P. Kamat,et al.  Charge Distribution between UV-Irradiated TiO2 and Gold Nanoparticles: Determination of Shift in the Fermi Level , 2003 .

[34]  Zili Wu,et al.  One-Step Synthesis of Nb2 O5 /C/Nb2 C (MXene) Composites and Their Use as Photocatalysts for Hydrogen Evolution. , 2018, ChemSusChem.

[35]  Xin Wang,et al.  Ultrathin molybdenum disulfide/carbon nitride nanosheets with abundant active sites for enhanced hydrogen evolution. , 2018, Nanoscale.

[36]  Wei Chen,et al.  Synthesis and Photocatalytic Activity of Calcium Antimony Oxide Hydroxide for the Degradation of Dyes in Water , 2009 .

[37]  Yi‐Jun Xu,et al.  Improving the visible light photoactivity of In2S3-graphene nanocomposite via a simple surface charge modification approach. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[38]  Liyi Shi,et al.  Design and synthesis of NiCe@m-SiO2 yolk-shell framework catalysts with improved coke- and sintering-resistance in dry reforming of methane , 2016 .

[39]  Wei Huang,et al.  Interdiffusion Reaction-Assisted Hybridization of Two-Dimensional Metal-Organic Frameworks and Ti3C2Tx Nanosheets for Electrocatalytic Oxygen Evolution. , 2017, ACS nano.

[40]  G. Zeng,et al.  Clay‐Inspired MXene‐Based Electrochemical Devices and Photo‐Electrocatalyst: State‐of‐the‐Art Progresses and Challenges , 2018, Advanced materials.

[41]  Gengnan Li,et al.  Highly Efficiently Delaminated Single-Layered MXene Nanosheets with Large Lateral Size. , 2017, Langmuir : the ACS journal of surfaces and colloids.

[42]  Hangxun Xu,et al.  Controlled Intercalation and Chemical Exfoliation of Layered Metal-Organic Frameworks Using a Chemically Labile Intercalating Agent. , 2017, Journal of the American Chemical Society.

[43]  Majid Beidaghi,et al.  In situ environmental transmission electron microscopy study of oxidation of two-dimensional Ti3C2 and formation of carbon-supported TiO2 , 2014 .

[44]  G. Zeng,et al.  Graphene-based materials: fabrication, characterization and application for the decontamination of wastewater and wastegas and hydrogen storage/generation. , 2013, Advances in colloid and interface science.

[45]  Yi Tang,et al.  Enhanced Capacitive Performance Based on Diverse Layered Structure of Two-Dimensional Ti3C2 MXene with Long Etching Time , 2016 .

[46]  V. Presser,et al.  One-step synthesis of nanocrystalline transition metal oxides on thin sheets of disordered graphitic carbon by oxidation of MXenes. , 2014, Chemical communications.

[47]  M. Lu,et al.  Metal sulfide nanostructures: synthesis, properties and applications in energy conversion and storage , 2012 .

[48]  Jie Wang,et al.  Three-dimensional porous MXene/layered double hydroxide composite for high performance supercapacitors , 2016 .

[49]  G. Zeng,et al.  Photodeposition of metal sulfides on titanium metal–organic frameworks for excellent visible-light-driven photocatalytic Cr(VI) reduction , 2015 .

[50]  Kai Xiao,et al.  Atomic Defects in Monolayer Titanium Carbide (Ti3C2Tx) MXene. , 2016, ACS nano.

[51]  Zhong‐Yong Yuan,et al.  Applications of hierarchically structured porous materials from energy storage and conversion, catalysis, photocatalysis, adsorption, separation, and sensing to biomedicine. , 2016, Chemical Society reviews.

[52]  J. Caro,et al.  A Two-Dimensional Lamellar Membrane: MXene Nanosheet Stacks. , 2017, Angewandte Chemie.

[53]  Baozhong Liu,et al.  Unique lead adsorption behavior of activated hydroxyl group in two-dimensional titanium carbide. , 2014, Journal of the American Chemical Society.

[54]  G. Zeng,et al.  Synthesis and applications of novel graphitic carbon nitride/metal-organic frameworks mesoporous photocatalyst for dyes removal , 2015 .

[55]  Guonan Chen,et al.  Study on the photocatalytic degradation of methyl orange in water using Ag/ZnO as catalyst by liquid chromatography electrospray ionization ion-trap mass spectrometry , 2008, Journal of the American Society for Mass Spectrometry.

[56]  Xueqin Zuo,et al.  Computational studies on the structural, electronic and optical properties of graphene-like MXenes (M2CT2, M = Ti, Zr, Hf; T = O, F, OH) and their potential applications as visible-light driven photocatalysts , 2016 .

[57]  A. Cheetham,et al.  Topotactic reduction of oxide nanomaterials: unique structure and electronic properties of reduced TiO2nanoparticles , 2014 .

[58]  Yury Gogotsi,et al.  Dye adsorption and decomposition on two-dimensional titanium carbide in aqueous media , 2014 .

[59]  Bo Chen,et al.  2D Transition‐Metal‐Dichalcogenide‐Nanosheet‐Based Composites for Photocatalytic and Electrocatalytic Hydrogen Evolution Reactions , 2016, Advanced materials.

[60]  Hao Yu,et al.  (111) TiO2-x/Ti3C2: Synergy of active facets, interfacial charge transfer and Ti3+ doping for enhance photocatalytic activity , 2017 .

[61]  Chuncheng Chen,et al.  Semiconductor-mediated photodegradation of pollutants under visible-light irradiation. , 2010, Chemical Society reviews.

[62]  Libo Wang,et al.  Hydrothermal synthesis of TiO2/Ti3C2 nanocomposites with enhanced photocatalytic activity , 2015 .

[63]  Wenguang Tu,et al.  Plasmonic Bi nanoparticles and BiOCl sheets as cocatalyst deposited on perovskite-type ZnSn(OH)6 microparticle with facet-oriented polyhedron for improved visible-light-driven photocatalysis , 2017 .

[64]  Linggang Zhu,et al.  MXene: a promising photocatalyst for water splitting , 2016 .

[65]  Dmitri Golberg,et al.  Functionalized hexagonal boron nitride nanomaterials: emerging properties and applications. , 2016, Chemical Society reviews.

[66]  H. Lee,et al.  Thermoelectric properties of in-situ plasma spray synthesized sub-stoichiometry TiO2−x , 2016, Scientific Reports.

[67]  X. Tao,et al.  Pillared Structure Design of MXene with Ultralarge Interlayer Spacing for High-Performance Lithium-Ion Capacitors. , 2017, ACS nano.

[68]  Chang E. Ren,et al.  Flexible and conductive MXene films and nanocomposites with high capacitance , 2014, Proceedings of the National Academy of Sciences.

[69]  Aijun Du,et al.  Ti3C2 MXene co-catalyst on metal sulfide photo-absorbers for enhanced visible-light photocatalytic hydrogen production , 2017, Nature Communications.

[70]  Yury Gogotsi,et al.  25th Anniversary Article: MXenes: A New Family of Two‐Dimensional Materials , 2014, Advanced materials.

[71]  Yury Gogotsi,et al.  Flexible MXene/Graphene Films for Ultrafast Supercapacitors with Outstanding Volumetric Capacitance , 2017 .

[72]  Yichun Liu,et al.  One-dimensional hierarchical heterostructures of In₂S₃ nanosheets on electrospun TiO₂ nanofibers with enhanced visible photocatalytic activity. , 2013, Journal of hazardous materials.

[73]  Xing Zhang,et al.  Metal-free efficient photocatalyst for stable visible water splitting via a two-electron pathway , 2015, Science.

[74]  Xin Wang,et al.  Switching charge transfer of C3N4/W18O49 from type-II to Z-scheme by interfacial band bending for highly efficient photocatalytic hydrogen evolution , 2017 .

[75]  M. Shiraishi,et al.  Work function of carbon nanotubes , 2001 .

[76]  Jie Liang,et al.  Phosphorus- and Sulfur-Codoped g-C3N4: Facile Preparation, Mechanism Insight, and Application as Efficient Photocatalyst for Tetracycline and Methyl Orange Degradation under Visible Light Irradiation , 2017 .

[77]  Guangming Zeng,et al.  Three dimensional graphene based materials: Synthesis and applications from energy storage and conversion to electrochemical sensor and environmental remediation. , 2015, Advances in colloid and interface science.

[78]  Minshen Zhu,et al.  Photoluminescent Ti3C2 MXene Quantum Dots for Multicolor Cellular Imaging , 2017, Advanced materials.

[79]  Yury Gogotsi,et al.  Cation Intercalation and High Volumetric Capacitance of Two-Dimensional Titanium Carbide , 2013, Science.

[80]  Jixian Yang,et al.  A rapid azo dye decolorization of methyl orange by the foam zero‐valent nickel , 2018 .

[81]  P. Kent,et al.  Hybrid Density Functional Study of Structural and Electronic Properties of Functionalized \ce{Ti_{n+1}X_n} (X= C, N) monolayers , 2013, 1306.6936.

[82]  G. Zeng,et al.  In situ synthesis of In2S3@MIL-125(Ti) core–shell microparticle for the removal of tetracycline from wastewater by integrated adsorption and visible-light-driven photocatalysis , 2016 .

[83]  OH-terminated two-dimensional transition metal carbides and nitrides as ultralow work function materials , 2015, 1507.04953.

[84]  Cheng Sun,et al.  Fabrication of a novel p–n heterojunction photocatalyst n-BiVO4@p-MoS2 with core–shell structure and its excellent visible-light photocatalytic reduction and oxidation activities , 2016 .

[85]  Yury Gogotsi,et al.  2D metal carbides and nitrides (MXenes) for energy storage , 2017 .

[86]  H. Kisch.  Semiconductor Photocatalysis for Chemoselective Radical Coupling Reactions. , 2017, Accounts of chemical research.