Tuning electrode surface electronics with thin layers

Patent metadata

Field	Value
Publication number	US-2018087164-A1
Application number	US-201715718943-A
Country	US
Kind code	A1
Filing date	Sep 28, 2017
Priority date	Sep 28, 2016
Publication date	Mar 29, 2018
Grant date	—

Abstract

The disclosure provides for thin films that can be used to tune the catalytic characteristics of heterogeneous electrocatalysts.

First claim

What is claimed is:

1 . A method to manufacture a heterogeneous electrocatalyst that has improved electrocatalytic activity for an electrochemical reaction, comprising:
layering or depositing one or more thin films of one or more conductive and/or semiconductive catalytic materials onto a surface of a conductive electrocatalytic substrate by using 1 to 100 cycles of an atomic layer deposition process, wherein the composition of the one of more thin films is different from the composition of the conductive electrocatalytic substrate, wherein the number of cycles of the atomic layer deposition process is used to tune the electrocatalytic activity of the heterogeneous electrocatalysts for the electrochemical reaction, and wherein the electrocatalytic activity of the heterogeneous electrocatalyst for the electrochemical reaction is improved in comparison to the electrocatalytic activity of the conductive electrocatalytic substrate.

2 . The method of claim 1 , wherein the one or more thin films are comprised of metals, alloys, metal oxides, metal nitrides, metal sulfides, metal fluorides, or a combination thereof.

3 . The method of claim 2 , wherein the one of more thin films comprise one or more metal oxides selected from Al 2 O 3 , NH 4 OSbW, Sb 2 O 5 , BaO, BaTiO 3 , BaZrO 3 , Al 6 BeO 10 , BeO, Bi 2 O 3 , Bi 2 O 5 , B 2 O 3 , CdO, CaO, Ce 2 O 3 , CeO 2 , CrO, Cr 2 O 3 , CrO 2 , CrO 3 , CoO, Co 2 O 3 , Cu 2 O 5 Yb 2 , Cu 2 O, CuFe 2 O 4 , CuO, GaO, Ga 2 O 3 , GeO, GeO 2 , Au 2 O, Au 2 O 3 , HfO 2 , In 2 O, InO, In 2 O 3 , Ir 2 O 3 , I rO 2 , Fe 3 O 4 , FeO, Fe 2 O 3 , PbO, PbO 2 , Li 2 O, Al 2 MgO 4 , MgO, Mn 3 O 4 , MnO, Mn 2 O 3 , MnO 2 , Mn 2 O 5 , Mn 2 O 7 , Hg 2 O, HgO, MoO 2 , MoO 3 , Mo 2 O 5 , NiFe 2 O 4 , NiO, Ni 2 O 3 , LiNbO 3 , NaNbO 3 , Nb 2 O 3 , Nb 2 O 5 , Os 2 O 3 , OsO 3 , OsO 4 , PdO, PdO 2 , (C 6 H 5 )AsO, Pt 3 O 4 , PtO, Pt 2 O 3 , K 2 O, Re 2 O 7 , ReO 4 , Rh 2 O 3 , Rb 2 O, RuO 2 , RuO 4 , SC 2 O 3 , Se 3 O 4 , Ag 2 O, Na 2 O, SrO, NaTaO 3 , Ta 2 O 3 , Ta 2 O 5 , SiO 2 , SnO, SnO 2 , SrTiO 3 , TiO, Ti 2 O 3 , TiO 2 , WCl 2 O 2 , W 2 O 3 , WO 2 , WO 3 , W 2 O 5 , VOCl 2 , VO, V 2 O 3 , VO 2 , V 2 O 5 , Yb 2 O 3 , YBa 2 Cu 3 O 7 , Y 2 O 3 , ZnO, ZrO 2 , fluorine doped tin oxide, iron doped titanium oxide, WO 3 doped ZnO, Fe doped CeO 2 , tin doped Fe 3 O 4 , and indium tin oxide.

4 . The method of claim 3 , wherein the one or more thin films comprise TiO 2 .

5 . The method of claim 1 , wherein 1 to 25 cycles of an atomic layer deposition process are used to deposit or layer one or more thin films onto a surface of the conductive electrocatalytic substrate.

6 . The method of claim 1 , wherein 1 to 15 cycles of an atomic layer deposition process are used to deposit or layer a thin film of TiO 2 onto a surface of the conductive electrocatalytic substrate.

7 . The method of claim 1 , wherein the one or more thin films are made from one or more precursors used in the atomic layer deposition process selected from aluminum tris(2,2,6,6-tetramethyl-3,5-heptanedionate), triisobutylaluminum, trimethylaluminum, tris(dimethylamido)aluminum(III), triphenylantimony(III), tris(dimethylamido)antimony(III), triphenylarsine, Triphenylarsine oxide, barium bis(2,2,6,6-tetramethyl-3,5-heptanedionate) hydrate, barium nitrate, Ba(C 9 H 23 N 3 ) 2 [C x H y C(O)CHC(O)C x H y ] 2 (x=3-4, y=2x+1), [Ba(C 5 (CH 3 ) 5 ) 2 ].2(C 4 H 8 O) , [Ba(C 5 (C 3 H 7 ) 3 H 2 ) 2 ].2(C 4 H 8 O) , bis (acetato-O) triphenylbismuth (V) , triphenylbismuth, tris(2-methoxyphenyl)bismuthine, triisopropyl borate, triphenylborane, tris(pentafluorophenyl)borane, cadmium acetylacetonate, calcium bis(6,6,7,7,8,8,8,-heptafluoro-2,2-dimethyl-3,5-octanedionate), calcium bis(2,2,6,6-tetramethyl-3,5-heptanedionate), bis(cyclopentadienyl)chromium(II), bis(pentamethylcyclopentadienyl)chromium(II), chromium(III) tris(2,2,6,6-tetramethyl-3,5-heptanedionate), bis(cyclopentadienyl)cobalt(II), bis(pentamethylcyclopentadienyl)cobalt(II), copper bis(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate), copper bis(2,2,6,6-tetramethyl-3,5-heptanedionate), tris(dimethylamido)gallium(III), germanium(IV) fluoride, hexaethyldigermanium(IV), tetramethylgermanium, tributylgermanium hydride, triethylgermanium hydride, triphenylgermanium hydride, bis(tert-butylcyclopentadienyl)dimethylhafnium(IV), bis(trimethylsilyl)amidohafnium(IV) chloride, dimethylbis(cyclopentadienyl)hafnium(IV), tetrakis(diethylamido)hafnium(IV), tetrakis(dimethylamido)hafnium(IV), tetrakis(ethylmethylamido)hafnium(IV), [1,1′-bis(diphenylphosphino)ferrocene]tetracarbonylmolybdenum(0), bis(pentamethylcyclopentadienyl)iron(II), 1,1′-diethylferrocene, iron(0) pentacarbonyl, iron(III) tris(2,2,6,6-tetramethyl-3,5-heptanedionate), bis(cyclopentadienyl)magnesium(II), bis(pentamethylcyclopentadienyl)magnesium, Mg(C 6 H 16 N 2 ) [C x H y C(O)CHC(O)C x H y ] 2 (x=3-4, y=2x+1), bis(pentamethylcyclopentadienyl)manganese(II), bis(tetramethylcyclopentadienyl)manganese(II), bromopentacarbonylmanganese(I), cyclopentadienylmanganese(I) tricarbonyl, ethylcyclopentadienylmanganese(I) tricarbonyl, manganese(0) carbonyl, (bicyclo[2.2.1]hepta-2,5-diene) tetracarbonylmolybdenum(0), bis(cyclopentadienyl)molybdenum(IV) dichloride, cyclopentadienylmolybdenum(II) tricarbonyl dimer, molybdenumhexacarbonyl, (propylcyclopentadienyl)molybdenum(I) tricarbonyl dimer, allyl(cyclopentadienyl)nickel(II), bis(cyclopentadienyl)nickel(II), bis(ethylcyclopentadienyl)nickel(II), nickel(II) bis(2,2,6,6-tetramethyl-3,5-heptanedionate), bis(cyclopentadienyl)niobium(IV) dichloride, trimethyl(methylcyclopentadienyl)platinum(IV), dirhenium decacarbonyl, (acetylacetonato) (1,5-cyclooctadiene)rhodium(I), (acetylacetonato) (1,5-cyclooctadiene)rhodium(I), bis(cyclopentadienyl)ruthenium(II), bis(ethylcyclopentadienyl)ruthenium(II), bis(pentamethylcyclopentadienyl)ruthenium(II), triruthenium dodecacarbonyl, Sr(C 9 H 23 N 3 ) 2 [C x H y C(O)CHC(O)C x H y ] 2 (x=3-4, y=2x+1), pentakis(dimethylamino)tantalum(V), tantalum(V) ethoxide, tris(diethylamido) (tert-butylimido)tantalum(V), tris(ethylmethylamido) (tert-butylimido)tantalum(V), Ta(C 2 H 5 O) 4 [C x H y C(O)CHC(O)C x Hy] 2 (x=3-4, y=2x+1), bis[bis(trimethylsilyl)amino]tin(II), dibutyldiphenyltin, hexaphenylditin(IV), tetraallyltin, tetrakis(diethylamido)tin(IV), tetramethyltin, tetravinyltin, tin(II) acetylacetonate, trimethyl(phenylethynyl)tin, trimethyl(phenyl)tin, tetrakis (dimethylamido)titanium(IV) (TDMAT), tetrakis(ethylmethylamido)titanium(IV), titanium(IV) diisopropoxidebis(2,2,6,6-tetramethyl-3,5-heptanedionate), titanium tetrachloride, titanium(IV) isopropoxide, Ti(OC 3 H 7 ) 2 [C x H y C(O)CHC(O)C x H y ] 2 (x=3-4, y=2x+1), bis(butylcyclopentadienyl)tungsten(IV) diiodide, bis(tert-butylimino)bis(tert-butylamino)tungsten, bis(tert-butylimino)bis(dimethylamino)tungsten(VI), bis(cyclopentadienyl)tungsten(IV) dichloride, bis(cyclopentadienyl)tungsten(IV) dihydride, bis(isopropylcyclopentadienyl)tungsten(IV) dihydride, cyclopentadienyltungsten(II) tricarbonyl hydride, tetracarbonyl(1,5-cyclooctadiene)tungsten(0), triamminetungsten(IV) tricarbonyl, tungsten hexacarbonyl, bis(cyclopentadienyl)vanadium(II), bis(cyclopentadienyl)vanadium(II), vanadium(V) oxytriisopropoxide, bis(pentafluorophenyl)zinc, bis(2,2,6,6-tetramethyl-3,5-heptanedionato)zinc(II), diethylzinc, and diphenylzinc.

8 . The method of claim 7 , wherein the one or more thin films are made from a precursor of tetrakis (dimethylamido)titanium(IV) used in the atomic layer deposition process.

9 . The method of claim 1 , wherein the conductive electrocatalytic substrate is at least 100 nm in thickness.

10 . The method of claim 1 , wherein the conductive electrocatalytic substrate is comprised of a conductive material, semiconduct

Assignees

• California Inst Of Techn

Inventors

• Finke Cody E
• Hoffmann Michael R
• Jasper Justin
• Kasmaee Laleh Majari
• Omelchenko Stefan

Classifications

• C02F2001/46142

  Catalytic coating · CPC title

• C02F1/4674 Primary

  with halogen or compound of halogens, e.g. chlorine, bromine · CPC title

• C25B11/0405

  Chemistry & Metallurgy · mapped topic

• C25B1/04

  by electrolysis of water · CPC title

• C23C16/405

  of refractory metals or yttrium · CPC title