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Journal ArticleDOI

Hierarchical “nanoroll” like MoS2/Ti3C2Tx hybrid with high electrocatalytic hydrogen evolution activity

01 Feb 2019-Applied Catalysis B-environmental (Elsevier)-Vol. 241, pp 89-94
TL;DR: In this article, a simple strategy to synthesize the hierarchical MoS2/Ti3C2Tx hybrid by combining liquid nitrogen-freezing and subsequent annealing was reported.
Abstract: Developing highly efficient noble-metal-free electrocatalysts for hydrogen evolution reaction (HER) has attracted increasing attentions. Here, we report a simple strategy to synthesize the hierarchical “nanoroll” like MoS2/Ti3C2Tx hybrid by combining liquid nitrogen-freezing and subsequent annealing. The quick freezing of the Ti3C2Tx nanosheets and ammonium tetrathiomolybdate mixture causes a sudden change in the strain of Ti3C2Tx, which leads to an interesting “nanoroll” like hierarchical structure. After annealing at H2/Ar atmosphere, vertically aligned molybdenum sulfide (MoS2) crystallites are in situ formed in and on the nanoroll like Ti3C2Tx. Notably, this hierarchical MoS2/Ti3C2Tx hybrid exhibits excellent HER catalytic activity with a small onset overpotential of 30 mV, and a more than 25-fold increase in the exchange current density compared with MoS2 was observed.
Citations
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Journal ArticleDOI
TL;DR: In this article, the state-of-the-art progress on MXene theory, materials synthesis techniques, morphology modifications, opto-electro-magnetic properties, and their applications are comprehensively discussed.

502 citations

Journal ArticleDOI
TL;DR: In this paper, a 2D-2D2D 2D structure of Ti3C2@TiOO2@MoS2 composite is achieved, which shows a remarkable enhancement in the photocatalytic H2 evolution reaction.
Abstract: Exposing the highly active facets and hybridizing the photocatalyst with appropriate cocatalysts with right placement have been regarded as a powerful approach to high performance photocatalysts. Herein, TiO2 nanosheets (NSs) are in situ grown on highly conductive Ti3C2 MXene and then MoS2 NSs are deposited on the (101) facets of TiO2 NSs with mainly exposed high-active (001) facets through a two-step hydrothermal method. And a unique 2D-2D-2D structure of Ti3C2@TiO2@MoS2 composite is achieved. With an optimized MoS2 loading amounts (15 wt%), the Ti3C2@TiO2@MoS2 composite shows a remarkable enhancement in the photocatalytic H2 evolution reaction compared with Ti3C2@TiO2 composite and TiO2 NS. It also shows good stability under the reaction condition. This arises from: (i) the in situ growth of TiO2 NSs construct strong interfacial contact with excellent electronic conductivity of Ti3C2, which facilitates the separation of carriers; (ii) the coexposed (101) and (001) facets can form a surface heterojunction within single TiO2 NS, which is beneficial for the transfer and separation of charge carriers; and (iii) the MoS2 NSs are deposited on the electrons-rich (101) facets of TiO2 NSs, which not only effectively reduces the charge carriers recombination rate by capturing photoelectrons, but also makes TiO2 NSs expose more highly active (001) facets to afford high-efficiency photogeneration of electron-hole pairs.

340 citations

Journal ArticleDOI
12 Aug 2020-ACS Nano
TL;DR: By clarifying the roles of individual material components in the MXene hybrids, this review provides design strategies to synergistically couple MXenes with associated materials for highly efficient and durable catalytic applications.
Abstract: Electro-, photo-, and photoelectrocatalysis play a critical role toward the realization of a sustainable energy economy. They facilitate numerous redox reactions in energy storage and conversion systems, enabling the production of chemical feedstock and clean fuels from abundant resources like water, carbon dioxide, and nitrogen. One major obstacle for their large-scale implementation is the scarcity of cost-effective, durable, and efficient catalysts. A family of two-dimensional transition metal carbides, nitrides, and carbonitrides (MXenes) has recently emerged as promising earth-abundant candidates for large-area catalytic energy storage and conversion due to their unique properties of hydrophilicity, high metallic conductivity, and ease of production by solution processing. To take full advantage of these desirable properties, MXenes have been combined with other materials to form MXene hybrids with significantly enhanced catalytic performances beyond the sum of their individual components. MXene hybridization tunes the electronic structure toward optimal binding of redox active species to improve intrinsic activity while increasing the density and accessibility of active sites. This review outlines recent strategies in the design of MXene hybrids for industrially relevant electrocatalytic, photocatalytic, and photoelectrocatalytic applications such as water splitting, metal-air/sulfur batteries, carbon dioxide reduction, and nitrogen reduction. By clarifying the roles of individual material components in the MXene hybrids, we provide design strategies to synergistically couple MXenes with associated materials for highly efficient and durable catalytic applications. We conclude by highlighting key gaps in the current understanding of MXene hybrids to guide future MXene hybrid designs in catalytic energy storage and conversion applications.

278 citations

Journal ArticleDOI
TL;DR: N-MoS2/CN possesses superior HER activity with an overpotential of 114 mV at 10 mA cm-2 and excellent stability over 10 h, delivering one of best MoS2-based HER electrocatalysts, and opens a new venue for optimizing materials with enhanced accessible catalytic sites for energy-related applications.
Abstract: The activity and accessibility of MoS2 edge sites are critical to deliver high hydrogen evolution reaction (HER) efficiency. Here, a porous carbon network confining ultrasmall N-doped MoS2 nanocrystals (N-MoS2/CN) is fabricated by a self-templating strategy, which realizes synergistically structural and electronic modulations of MoS2 edges. Experiments and density functional theory calculations demonstrate that the N dopants could activate MoS2 edges for HER, while the porous carbon network could deliver high accessibility of the active sites from N-MoS2 nanocrystals. Consequently, N-MoS2/CN possesses superior HER activity with an overpotential of 114 mV at 10 mA cm-2 and excellent stability over 10 h, delivering one of best MoS2-based HER electrocatalysts. Moreover, this study opens a new venue for optimizing materials with enhanced accessible catalytic sites for energy-related applications.

253 citations

Journal ArticleDOI
TL;DR: In this paper, the authors synthesized cobalt nanoleaves metal-organic framed work (MOF) on nickel foam substrate with uniform growth, and the as-prepared heterostructure (Co3O4/MoS2) can act as bifunctional electrocatalysts for overall water splitting.
Abstract: Fabrication of highly efficient, sustainable and low-cost nonprecious metal oxide for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is exceedingly challenging and warranted for overall water splitting. Herein, we synthesized cobalt nanoleaves metal-organic framed work (MOF) on nickel foam substrate with uniform growth. After calcination of Co-MOF, molybdenum disulfide nanosheets is grown by a facial hydrothermal method. The as-prepared heterostructure (Co3O4/MoS2) can act as bifunctional electrocatalysts for overall water splitting. Under optimized condition, synthesized Co3O4/MoS2 heterostructure catalyst exhibited excellent catalytic activity for both OER and HER in 1 M KOH solution with a current density of 20 mA cm−2 at overpotential of 230 mV for OER and 205 mV for HER (@ j = 10 mA cm−2) and Tafel slopes of 45 and 98 mV dec-1, respectively. The superior catalytic activity for both OER and HER arises from the unique heterostructure of Co3O4/MoS2 and the synergistic effects of Co3O4 and MoS2.

233 citations

References
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Journal ArticleDOI
06 Jul 2007-Science
TL;DR: The active site for hydrogen evolution, a reaction catalyzed by precious metals, on nanoparticulate molybdenum disulfide (MoS2) is determined by atomically resolving the surface of this catalyst before measuring electrochemical activity in solution.
Abstract: The identification of the active sites in heterogeneous catalysis requires a combination of surface sensitive methods and reactivity studies. We determined the active site for hydrogen evolution, a reaction catalyzed by precious metals, on nanoparticulate molybdenum disulfide (MoS2) by atomically resolving the surface of this catalyst before measuring electrochemical activity in solution. By preparing MoS2 nanoparticles of different sizes, we systematically varied the distribution of surface sites on MoS2 nanoparticles on Au(111), which we quantified with scanning tunneling microscopy. Electrocatalytic activity measurements for hydrogen evolution correlate linearly with the number of edge sites on the MoS2 catalyst.

4,930 citations

Journal ArticleDOI
TL;DR: More than twenty 2D carbides, nitrides and carbonitrides of transition metals (MXenes) have been synthesized and studied, and dozens more predicted to exist.
Abstract: The family of 2D transition metal carbides, carbonitrides and nitrides (collectively referred to as MXenes) has expanded rapidly since the discovery of Ti3C2 in 2011. The materials reported so far always have surface terminations, such as hydroxyl, oxygen or fluorine, which impart hydrophilicity to their surfaces. About 20 different MXenes have been synthesized, and the structures and properties of dozens more have been theoretically predicted. The availability of solid solutions, the control of surface terminations and a recent discovery of multi-transition-metal layered MXenes offer the potential for synthesis of many new structures. The versatile chemistry of MXenes allows the tuning of properties for applications including energy storage, electromagnetic interference shielding, reinforcement for composites, water purification, gas- and biosensors, lubrication, and photo-, electro- and chemical catalysis. Attractive electronic, optical, plasmonic and thermoelectric properties have also been shown. In this Review, we present the synthesis, structure and properties of MXenes, as well as their energy storage and related applications, and an outlook for future research. More than twenty 2D carbides, nitrides and carbonitrides of transition metals (MXenes) have been synthesized and studied, and dozens more predicted to exist. Highly electrically conductive MXenes show promise in electrical energy storage, electromagnetic interference shielding, electrocatalysis, plasmonics and other applications.

4,745 citations

Journal ArticleDOI
TL;DR: In this article, a selective solvothermal synthesis of MoS2 nanoparticles on reduced graphene oxide (RGO) sheets suspended in solution was developed, which exhibited superior electrocatalytic activity in the hydrogen evolution reaction (HER).
Abstract: Advanced materials for electrocatalytic and photoelectrochemical water splitting are central to the area of renewable energy. In this work, we developed a selective solvothermal synthesis of MoS2 nanoparticles on reduced graphene oxide (RGO) sheets suspended in solution. The resulting MoS2/RGO hybrid material possessed nanoscopic few-layer MoS2 structures with an abundance of exposed edges stacked onto graphene, in strong contrast to large aggregated MoS2 particles grown freely in solution without GO. The MoS2/RGO hybrid exhibited superior electrocatalytic activity in the hydrogen evolution reaction (HER) relative to other MoS2 catalysts. A Tafel slope of ∼41 mV/decade was measured for MoS2 catalysts in the HER for the first time; this exceeds by far the activity of previous MoS2 catalysts and results from the abundance of catalytic edge sites on the MoS2 nanoparticles and the excellent electrical coupling to the underlying graphene network. The ∼41 mV/decade Tafel slope suggested the Volmer–Heyrovsky mec...

4,370 citations

Journal ArticleDOI
04 Dec 2014-Nature
TL;DR: This capacitance report reports a method of producing two-dimensional titanium carbide ‘clay’ using a solution of lithium fluoride and hydrochloric acid that offers a much faster route to film production as well as the avoidance of handling hazardous concentrated hydrofluoric acid.
Abstract: Safe and powerful energy storage devices are becoming increasingly important. Charging times of seconds to minutes, with power densities exceeding those of batteries, can in principle be provided by electrochemical capacitors--in particular, pseudocapacitors. Recent research has focused mainly on improving the gravimetric performance of the electrodes of such systems, but for portable electronics and vehicles volume is at a premium. The best volumetric capacitances of carbon-based electrodes are around 300 farads per cubic centimetre; hydrated ruthenium oxide can reach capacitances of 1,000 to 1,500 farads per cubic centimetre with great cyclability, but only in thin films. Recently, electrodes made of two-dimensional titanium carbide (Ti3C2, a member of the 'MXene' family), produced by etching aluminium from titanium aluminium carbide (Ti3AlC2, a 'MAX' phase) in concentrated hydrofluoric acid, have been shown to have volumetric capacitances of over 300 farads per cubic centimetre. Here we report a method of producing this material using a solution of lithium fluoride and hydrochloric acid. The resulting hydrophilic material swells in volume when hydrated, and can be shaped like clay and dried into a highly conductive solid or rolled into films tens of micrometres thick. Additive-free films of this titanium carbide 'clay' have volumetric capacitances of up to 900 farads per cubic centimetre, with excellent cyclability and rate performances. This capacitance is almost twice that of our previous report, and our synthetic method also offers a much faster route to film production as well as the avoidance of handling hazardous concentrated hydrofluoric acid.

3,783 citations

Journal ArticleDOI
27 Sep 2013-Science
TL;DR: This study demonstrates the spontaneous intercalation of cations from aqueous salt solutions between two-dimensional (2D) Ti3C2 MXene layers, and provides a basis for exploring a large family of 2D carbides and carbonitrides in electrochemical energy storage applications using single- and multivalent ions.
Abstract: The intercalation of ions into layered compounds has long been exploited in energy storage devices such as batteries and electrochemical capacitors However, few host materials are known for ions much larger than lithium We demonstrate the spontaneous intercalation of cations from aqueous salt solutions between two-dimensional (2D) Ti3C2 MXene layers MXenes combine 2D conductive carbide layers with a hydrophilic, primarily hydroxyl-terminated surface A variety of cations, including Na+, K+, NH4+, Mg2+, and Al3+, can also be intercalated electrochemically, offering capacitance in excess of 300 farads per cubic centimeter (much higher than that of porous carbons) This study provides a basis for exploring a large family of 2D carbides and carbonitrides in electrochemical energy storage applications using single- and multivalent ions

3,018 citations