Functionalization of Two‐Dimensional Transition‐Metal Dichalcogenides

Two-dimensional (2D) layered transition-metal dichalcogenides (TMDs) are a fascinating class of nanomaterials that have the potential for application in catalysis, electronics, photonics, energy storage, and sensing. TMDs are rather inert, and thus pose problems for chemical derivatization. However, to further modify the properties of TMDs and fully harness their capabilities, routes towards their chemical functionalization must be identified. Herein, recent efforts toward the chemical (bond-forming) functionalization of 2D TMDs are critically reviewed. Recent successes are highlighted, along with areas where further detailed analyses and experimentation are required. This burgeoning field is very much in its infancy but has already provided several important breakthroughs.

[1]  L. David,et al.  Polymer-Derived Ceramic Functionalized MoS2 Composite Paper as a Stable Lithium-Ion Battery Electrode , 2015, Scientific Reports.

[2]  Yu-Chuan Lin,et al.  Growth of large-area and highly crystalline MoS2 thin layers on insulating substrates. , 2012, Nano letters.

[3]  C. Brinker,et al.  Controlling the metal to semiconductor transition of MoS2 and WS2 in solution. , 2015, Journal of the American Chemical Society.

[4]  J. Coleman,et al.  Two-Dimensional Nanosheets Produced by Liquid Exfoliation of Layered Materials , 2011, Science.

[5]  Qiang Sun,et al.  Structures and Phase Transition of a MoS2 Monolayer , 2014 .

[6]  Jonathan N. Coleman,et al.  Basal-Plane Functionalization of Chemically Exfoliated Molybdenum Disulfide by Diazonium Salts. , 2015, ACS nano.

[7]  S. C. Moss,et al.  Anisotropic mean-square displacements (MSD) in single-crystals of 2H- and 3R-MoS2 , 1983 .

[8]  R. Kaner,et al.  Honeycomb carbon: a review of graphene. , 2010, Chemical reviews.

[9]  M. Kanatzidis,et al.  Exfoliated and Restacked MoS2 and WS2: Ionic or Neutral Species? Encapsulation and Ordering of Hard Electropositive Cations , 1999 .

[10]  Zhi-Man Bai,et al.  Surface functionalization of MoS2 with POSS for enhancing thermal, flame-retardant and mechanical properties in PVA composites , 2014 .

[11]  Towards intrinsic charge transport in monolayer molybdenum disulfide by defect and interface engineering. , 2014, Nature communications.

[12]  Y. Chui,et al.  Salt-assisted high-throughput synthesis of single- and few-layer transition metal dichalcogenides and their application in organic solar cells. , 2014, Small.

[13]  M. Aono,et al.  Selective Adsorption of Thiol Molecules at Sulfur Vacancies on MoS2(0001), Followed by Vacancy Repair via S–C Dissociation , 2012 .

[14]  Minho Yang,et al.  High density decoration of noble metal nanoparticles on polydopamine-functionalized molybdenum disulphide. , 2015, Journal of colloid and interface science.

[15]  J. Coleman,et al.  Liquid Exfoliation of Layered Materials , 2013, Science.

[16]  Hongzheng Chen,et al.  Graphene-like two-dimensional materials. , 2013, Chemical reviews.

[17]  Andre K. Geim,et al.  Electric Field Effect in Atomically Thin Carbon Films , 2004, Science.

[18]  Liang Cheng,et al.  Drug Delivery with PEGylated MoS2 Nano‐sheets for Combined Photothermal and Chemotherapy of Cancer , 2014, Advanced materials.

[19]  Zhiyuan Zeng,et al.  Single-layer semiconducting nanosheets: high-yield preparation and device fabrication. , 2011, Angewandte Chemie.

[20]  Hua Zhang,et al.  The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets. , 2013, Nature chemistry.

[21]  Benzhao He,et al.  A general one-step approach for in situ decoration of MoS2 nanosheets with inorganic nanoparticles , 2015 .

[22]  Andre K. Geim,et al.  The rise of graphene. , 2007, Nature materials.

[23]  Nian Bing Li,et al.  Hemin-functionalized MoS2 nanosheets: enhanced peroxidase-like catalytic activity with a steady state in aqueous solution , 2014 .

[24]  P. D. Fleischauer,et al.  Electronic Structure and Lubrication Properties of MoS2: a Qualitative Molecular Orbital Approach , 1989 .

[25]  Jakob Kibsgaard,et al.  Size threshold in the dibenzothiophene adsorption on MoS2 nanoclusters. , 2010, ACS nano.

[26]  Andre K. Geim,et al.  Two-dimensional atomic crystals. , 2005, Proceedings of the National Academy of Sciences of the United States of America.

[27]  Weibo Cai,et al.  Iron oxide decorated MoS2 nanosheets with double PEGylation for chelator-free radiolabeling and multimodal imaging guided photothermal therapy. , 2015, ACS nano.

[28]  Y. Shao,et al.  Direct detection of DNA below ppb level based on thionin-functionalized layered MoS2 electrochemical sensors. , 2014, Analytical chemistry.

[29]  Hee‐Tae Jung,et al.  Tunable volatile organic compounds sensor by using thiolated ligand conjugation on MoS2. , 2014, Nano letters.

[30]  P. Laplace,et al.  Functionalization of liquid-exfoliated two-dimensional 2H-MoS2. , 2015, Angewandte Chemie.

[31]  Takhee Lee,et al.  Electrical and Optical Characterization of MoS2 with Sulfur Vacancy Passivation by Treatment with Alkanethiol Molecules. , 2015, ACS nano.

[32]  E. Johnston-Halperin,et al.  Progress, challenges, and opportunities in two-dimensional materials beyond graphene. , 2013, ACS nano.

[33]  P. Miró,et al.  An atlas of two-dimensional materials. , 2014, Chemical Society reviews.

[34]  Martin Pumera,et al.  Covalent functionalization of MoS2 , 2016 .

[35]  Mrinmoy De,et al.  Ligand conjugation of chemically exfoliated MoS2. , 2013, Journal of the American Chemical Society.

[36]  Wenxin Zhu,et al.  A one-step approach to the large-scale synthesis of functionalized MoS2 nanosheets by ionic liquid assisted grinding. , 2015, Nanoscale.

[37]  Takeshi Fujita,et al.  Covalent functionalization of monolayered transition metal dichalcogenides by phase engineering. , 2015, Nature chemistry.

[38]  C. Rao,et al.  Graphene analogues of inorganic layered materials. , 2013, Angewandte Chemie.

[39]  L. Mattheiss Band Structures of Transition-Metal-Dichalcogenide Layer Compounds. , 1973 .

[40]  W. Schreiner,et al.  Single-Step Exfoliation and Covalent Functionalization of MoS2 Nanosheets by an Organosulfur Reaction. , 2015, Chemistry.

[41]  Ruitao Lv,et al.  Transition metal dichalcogenides and beyond: synthesis, properties, and applications of single- and few-layer nanosheets. , 2015, Accounts of chemical research.

[42]  Benjamin J. Carey,et al.  Electronic Tuning of 2D MoS2 through Surface Functionalization , 2015, Advanced materials.

[43]  Mustafa Lotya,et al.  Large‐Scale Exfoliation of Inorganic Layered Compounds in Aqueous Surfactant Solutions , 2011, Advanced materials.

[44]  E. Benavente,et al.  Intercalation chemistry of molybdenum disulfide , 2002 .

[45]  Jinmao You,et al.  A novel aptamer-functionalized MoS2 nanosheet fluorescent biosensor for sensitive detection of prostate specific antigen , 2014, Analytical and Bioanalytical Chemistry.

[46]  H. Jeong,et al.  Functional polyelectrolyte nanospaced MoS2 multilayers for enhanced photoluminescence. , 2014, Nano letters.

[47]  M. Otyepka,et al.  Functionalization of graphene: covalent and non-covalent approaches, derivatives and applications. , 2012, Chemical reviews.

[48]  J. Coleman Liquid exfoliation of defect-free graphene. , 2013, Accounts of chemical research.

[49]  Jie Yu,et al.  High-throughput synthesis of single-layer MoS2 nanosheets as a near-infrared photothermal-triggered drug delivery for effective cancer therapy. , 2014, ACS nano.