Single-atomically dispersed metal / unconventional-phase transition-metal dichalcogenide nanosheet hybrids and methods of preparation and use thereof

Abstract

A single-atomically dispersed metal/two-dimensional transition-metal dichalcogenide nanosheet hybrid comprising a plurality of single-atomically dispersed metal atoms disposed on at least one surface of a transition-metal dichalcogenide nanosheet, wherein the transition-metal dichalcogenide nanosheet is uniformly crystalline.

What is claimed is: 
     
         1 . A single-atomically dispersed metal/two-dimensional transition-metal dichalcogenide nanosheet hybrid (TMD NS hybrid) comprising a plurality of single-atomically dispersed metal atoms disposed on at least one surface of a transition-metal dichalcogenide nanosheet (TMD NS), wherein the transition-metal dichalcogenide nanosheet is uniformly crystalline. 
     
     
         2 . The TMD NS hybrid of  claim 1 , wherein each of the plurality of single-atomically dispersed metal atoms is ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, gold, iron, cobalt, nickel, copper, zinc, cadmium, indium, tin, antimony, lead, bismuth, or other metal atoms. 
     
     
         3 . The TMD NS hybrid of  claim 1 , wherein each of the plurality of single-atomically dispersed metal atoms is platinum, gold, nickel, iridium, silver, tin, bismuth, or copper. 
     
     
         4 . The TMD NS hybrid of  claim 1 , wherein the TMD NS comprises MoS 2 , MoSe 2 , MoTe 2 , WS 2 , WSe 2 , MoTe 2 , WTe 2 , TiS 2 , TiSe 2 , TaS 2 , TaSe 2 , VS 2 , VSe 2 , NbS 2 , NbSe 2 , ReS 2 , ReSe 2 , MoS 2(1-A) Se 2A , or WS 2(1-A) Se 2A , wherein A is 0-1. 
     
     
         5 . The TMD NS hybrid of  claim 4 , wherein the crystal phase of the transition-metal dichalcogenide is 1T′ phase. 
     
     
         6 . The TMD NS hybrid of  claim 1 , wherein the TMD NS comprises 1T′-MoS 2 , 1T′-MoSe 2 , 1T′-MoSSe, or 1T′-WS 2 . 
     
     
         7 . The TMD NS hybrid of  claim 1 , wherein the TMD NS comprises 1T′-MoS 2 . 
     
     
         8 . The TMD NS hybrid of  claim 1 , wherein each of the plurality of single-atomically dispersed metal atoms is platinum, gold, nickel, iridium, silver, tin, bismuth, or copper and the TMD NS comprises 1T′-MoS 2 , 1T′-MoSe 2 , 1T′-MoSSe, or 1T′-WS 2 . 
     
     
         9 . The TMD NS hybrid of  claim 1 , wherein each of the plurality of single-atomically dispersed metal atoms is platinum and the TMD NS comprises 1T′-MoS 2 . 
     
     
         10 . The TMD NS hybrid of  claim 1 , wherein the plurality of single-atomically dispersed metal atoms is present in the TMD NS hybrid at a weight percentage of 12.2 wt % or less. 
     
     
         11 . The TMD NS hybrid of  claim 1 , wherein the plurality of single-atomically dispersed metal atoms are present in the TMD NS hybrid at a weight percentage of 10.0 wt % or less. 
     
     
         12 . The TMD NS hybrid of  claim 1 , wherein each of the plurality of single-atomically dispersed metal atoms is gold or platinum; the TMD NS comprises 1T′-MoS 2 ; and the plurality of single-atomically dispersed metal atoms are present in the TMD NS hybrid at a weight percentage of 10.0 wt % or less. 
     
     
         13 . A method of preparing the TMD NS hybrid of  claim 1 , the method comprising: contacting a TMD NS with a plurality of single-atomically dispersed metal atom precursors in the presence of a reducing agent thereby forming the TMD NS hybrid, TMD NS is uniformly crystalline. 
     
     
         14 . The method of  claim 13 , wherein each of the plurality of single-atomically dispersed metal atom precursors are metal salts comprising at least one metal atom. 
     
     
         15 . The method of  claim 13 , wherein the plurality of single-atomically dispersed metal atom precursors is selected from the group consisting of M 2 PtX 4 , M 2 PtX 6 , M 2 IrX 6 , MAuX 4 , SnY 3 , BiY 3 , CuY 2 , AgY, NiY, wherein X is halide and Y is nitrate, cyanide, formate, acetate, or acetylacetonate; and M is hydrogen, lithium, sodium, potassium, or cesium. 
     
     
         16 . The method of  claim 13 , wherein the reducing agent is ascorbic acid, sodium citrate, metal hydride, H 2 , hydrazine, alcohol, organolithium, electrochemical reduction, or photoreduction optionally in the presence of an additional reducing agent. 
     
     
         17 . The method of  claim 13 , wherein the plurality of single-atomically dispersed metal atom precursors is K 2 PtCl 4 , H 2 IrCl 6 , HAuCl 4 , SnCl 3 , BiCl 3 , CuCl 2 , AgNO 3 , or NiNO 3 , and the reducing agent is photoreduction in the presence of an alcohol or chemical reduction by using n-butyllithium as reducing agent. 
     
     
         18 . The method of  claim 17 , wherein the plurality of single-atomically dispersed metal atoms are present in the TMD NS hybrid at a weight percentage of 10.0 wt % or less. 
     
     
         19 . An electrode comprising a base electrode and the TMD NS hybrid of  claim 1 , wherein the base electrode is a planar electrode, including the glassy carbon electrode, a graphite electrode, an indium tin oxide (ITO) electrode, a fluorine doped tin oxide (FTO) electrode, a gas diffusion electrode (GDE), carbon paper electrode, carbon fiber electrode, polycarbonate track etch (PCTE)-based electrode, or titanium-based electrode. 
     
     
         20 . An electrochemical cell comprising: a cathode comprising the TMD NS hybrid of  claim 1 ; an anode; and an electrolyte. 
     
     
         21 . A method of producing hydrogen gas, the method comprising reducing a proton source at the cathode of the electrochemical cell of  claim 20  thereby producing hydrogen gas, wherein the proton source is water optionally comprising an acid.