IP Library › Granted Patent US 12,043,553

Granted Patent B2

US 12,043,553 · App. 17/084,746 · Granted Jul 23, 2024

Quantum material/vanadium oxide heterostructures, methods of making same, and uses thereof

Inventors: Sarbajit Banerjee (College Station, TX); David F. Watson (Williamsville, NY); Justin L. Andrews (West Lafayette, IN); Junsang Cho (Mishawaka, IN); Nuwanthi Suwandaratne (Amherst, NY); Aaron Sheng (Buffalo, NY)

Assignees: THE TEXAS A&M UNIVERSITY SYSTEM; THE RESEARCH FOUNDATION FOR THE STATE UNIVERSITY OF NEW YORK

C01G31/02 C01G19/02 C01G53/40 C25B1/02 C25B1/55 B82Y30/00 B82Y40/00 C01P2004/16 C01P2004/61 C01P2004/62 C01P2004/64 C01P2004/82 C01P2006/40

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Quick Facts

Patent No.: US 12,043,553
App. No.: 17/084,746
Granted: Jul 23, 2024
Kind: B2

External Links

USPTO Patent Center↗ Full Patent PDF↗

Abstract

The subject invention pertains to the synthesis and characterization of V 2 O 5 /CdE NW/QD heterostructures. The V 2 O 5 /CdE heterostructures are versatile new materials constructs for light harvesting, charge separation, and the photocatalytic production of solar fuels; polymorphism of V 2 O 5 and compositional alloying of both components provides for a substantial design space for tuning of interfacial energy offsets. Also provided are a new class of type-II heterostructures composed of cadmium chalcogenide QDs (CdE where E=S, Se, or Te) and α-V 2 O 5 nanowires (NWs). The synthesis and characterization of V 2 O 5 /CdE NW/QD heterostructures, prepared via successive ionic layer adsorption and reaction (SILAR) and linker-assisted assembly (LAA), the characterization of their photoinduced charge-transfer reactivity using transient absorption spectroscopy, and their performance in the photocatalytic reduction of protons to hydrogen are also disclosed.

Claims (488)

1. A composition comprising a M x V 2 O 5 material, said composition comprising Ni x V 2 O 5 , Pb x V 2 O 5 , Co x V 2 O 5 , Zn x V 2 O 5 , Sn x V 2 O 5 , Hg x V 2 O 5 , Tl x V 2 O 5 , Ga x V 2 O 5 , In x V 2 O 5 , or a combination thereof, where x is 0.0000001 to 0.67, provided that in the case of Pb x V 2 O 5 , x may not be 0.27-0.33, wherein the composition comprises a plurality of quantum dots or a quantum-confined thin film disposed on at least a portion of the surface of the M x V 2 O 5 material.

2. The composition of claim 1 , wherein the composition has the following nominal composition: Ni 0.331 V 2 O 5 or Sn 0.23 V 2 O 5 .

3. The composition of claim 1 , wherein the composition has the following structure:

i) lattice parameters, and atom positions for Sn 0.225 V 2 O 5

a = 15.339(2) Å; b = 3.6217(3) Å; c = 10.0781(8) Å;

β = 109.829(7)°; V = 526.67(6) Å 3 ;

χ 2 = 6.147; Rw = 6.52%; wRp = 8.96%

Atom

Occupancy

Uiso

Sn(1)

1.0095(12)

0.00

0.412(2)

0.225(6)

0.006

V(1)

0.1189(8)

0.00

0.1209(11)

1.0

0.008

V(2)

0.3511(9)

0.00

0.1032(14)

1.0

0.008

V(3)

0.2965(8)

0.00

0.4175(13)

1.0

0.008

O(1)

0.00(0)

1.0

0.015

O(2)

0.0958(25)

0.00

0.285(4)

1.0

0.015

O(3)

0.1529(24)

0.50

0.095(4)

1.0

0.015

O(4)

0.2533(24)

0.00

0.214(4)

1.0

0.015

O(5)

0.4482(23)

0.00

0.254(4)

1.0

0.015

O(6)

0.3258(23)

0.50

0.0228(33)

1.0

0.015

O(7)

0.4129(27)

0.00

0.518(4)

1.0

0.015

O(8)

0.2748

0.50

0.3861

1.0

0.015

and/or

bond angles and lengths for MO x polyhedra for Sn 0.225 V 2 O 5

V—O Polyhedra

V—O

Distance (Å)

O—V—O

Angle (°)

V(1)O 6 Octahedra

V(1)—O(1)

1.818(10)

O(1)—V(1)—O(3)

99.5(11)

O(1)—V(1)—O(4)

167.9(14)

V(1)—O(2)

1.81(4)

O(1)—V(1)—O(6)

95.4(10)

O(2)—V(1)—O(3)

105.8(11)

V(1)—O(3)

1.927(13)

O(2)—V(1)—O(3)

105.8(11)

O(2)—V(1)—O(4)

93.5(15)

V(1)—O(3)

1.927(13)

O(2)—V(1)—O(6)

166.0(16)

O(3)—V(1)—O(3)

140.0(22)

V(1)—O(4)

1.954(35)

O(3)—V(1)—O(4)

77.1(12)

O(3)—V(1)—O(6)

71.7(12)

V(1)—O(6)

1.91(4)

O(3)—V(1)—O(4)

77.1(11)

O(3)—V(1)—O(3)

71.7(11)

O(4)—V(1)—O(6)

72.5(15)

V(2)O 6 Octahedra

V(2)—O(3)

1.98(4)

O(3)—V(2)—O(4)

137.4(13)

O(3)—V(2)—O(5)

127.5(21)

V(2)—O(4)

2.15(4)

O(3)—V(2)—O(6)

69.5(10)

O(3)—V(2)—O(6)

69.5(10)

V(2)—O(5)

1.730(28)

O(4)—V(2)—O(5)

95.0(18)

O(4)—V(2)—O(6)

98.0(14)

V(2)—O(6)

1.968(13)

O(4)—V(2)—O(6)

98.0(14)

O(5)—V(2)—O(6)

110.6(10)

V(2)—O(6)

1.968(13)

O(5)—V(2)—O(6)

110.6(10)

V(2)—O(6)

2.576(26)

O(5)—V(2)—O(6)

133.9(17)

V(3)O 5

V(3)—O(4)

1.926(35)

O(4)—V(3)—O(7)

122.5(16)

Square Pyramid

V(3)—O(7)

1.728(30)

O(4)—V(3)—O(7)

80.8(4)

V(3)—O(8)

1.8490(24)

O(4)—V(3)—O(8)

80.8(4)

V(3)—O(8)

1.8490(24)

O(7)—V(3)—O(8)

100.98(34)

V(3)—O(8)

2.565(12)

O(7)—V(3)—O(8)

100.98(34)

O(8)—V(3)—O(8)

156.7(7)

Sn(1)O 7

Sn(1)—O(2)

2.13(5)

O(2)—Sn(1)—O(5)

77.4(12)

Distorted

O(2)—Sn(1)—O(5)

77.4(12)

pentagonal

Sn(1)—O(5)

2.385(24)

O(2)—Sn(1)—O(7)

79.0(12)

bipyramid

O(2)—Sn(1)—O(7)

79.0(12)

Sn(1)—O(5)

2.385(24)

O(5)—Sn(1)—O(5)

98.8(13)

Sn(1)—O(7)

2.771(31)

O(5)—Sn(1)—O(7)

68.2(9)

Sn(1)—O(7)

2.771(31)

O(5)—Sn(1)—O(7)

155.1(17)

Sn(1)—O(7)

2.150(19)

O(5)—Sn(1)—O(7)

68.2(9)

Sn(1)—O(7)

2.150(19)

O(7)—Sn(1)—O(7)

114.7(16)

ii) lattice parameters, and atom positions for β-Ni 0.333 V 2 O 5

a = 15.3711(7) Å, b = 3.6100(1) Å, c = 10.0726(5) Å,

β = 109.968(4) Å, V = 525.34(3) Å 3

χ 2 = 6.379, Rw = 4.85%, wRp = 6.81%

Atom

Occupancy

Uiso

Ni(1)

1.0042

0.000(0)

0.3926(11)

0.507(5)

0.008

V(1)

0.1240(5)

0.000(0)

0.1138(7)

1.0

0.008

V(2)

0.3392(4)

0.000(0)

0.1067(6)

1.0

0.008

V(3)

0.2881(5)

0.000(0)

0.4234(6)

1.0

0.008

O(1)

0.0000(0)

0.000(0)

0.0000(0)

1.0

0.0126

O(2)

0.1083(15)

0.000(0)

0.2653(19)

1.0

0.0126

O(3)

0.1321(16)

0.500(0)

0.0555(19)

1.0

0.0126

O(4)

0.2860(15)

0.000(0)

0.2501(21)

1.0

0.0126

O(5)

0.4400(13)

0.000(0)

0.2324(21)

1.0

0.0126

O(6)

0.3129(14)

0.500(0)

0.1005(21)

1.0

0.0126

O(7)

0.4083(14)

0.000(0)

0.4670(18)

1.0

0.0126

O(8)

0.2496(19)

0.500(0)

0.4100(0)

1.0

0.0126

and/or

bond angles and lengths for β-Ni 0.331 V 2 O 5

V—O Polyhedra

V—O

Distance (Å)

O—V—O

Angle (°)

V(1)O 6 Octahedra

V(1)—O(1)

1.859(7)

O(1)—V(1)—O(2)

97.4(9)

V(1)—O(2)

1.624(18)

O(1)—V(1)—O(3)

88.3(7)

V(1)—O(3)

1.915(7)

88.3(7)

V(1)—O(3)

1.915(7)

O(2)—V(1)—O(3)

109.5(6)

V(1)—O(4)

2.267(18)

109.5(6)

V(1)—O(6)

2.65127(12)

O(3)—V(1)—O(3)

140.9(12)

V(2)O 6 Octahedra

V(2)—O(3)

1.832(20)

O(3)—V(2)—O(4)

169.0(11)

O(3)—V(2)—O(5)

103.7(11)

V(2)—O(4)

1.888(20)

O(3)—V(2)—O(6)

95.0(8)

V(2)—O(5)

1.632(18)

O(4)—V(2)—O(5)

87.2(9)

O(4)—V(2)—O(6)

83.0(7)

V(2)—O(6)

1.846(5)

83.0(7)

O(5)—V(2)—O(6)

99.5(7)

V(2)—O(6)

1.846(5)

99.5(7)

V(2)—O(6)

2.548(17)

155.8(14)

V(3)O 5

V(3)—O(4)

2.872(11)

O(4)—V(3)—O(7)

84.7(9)

Square pyramid

V(3)—O(7)

2.872(11)

O(4)—V(3)—O(8)

91.75(27)

V(3)—O(8)

1.8903(20)

162.8(8)

V(3)—O(8)

1.8903(20)

O(7)—V(3)—O(8)

107.27(20)

V(3)—O(8)

1.953(7)

112.5(7)

O(8)—V(3)—O(8)

145.4(4)

83.31(21)

Ni(1)O 7

Ni(1)—O(2)

2.368(24)

O(2)—Ni(1)—O(7)

135.33(34)

Pentagonal

Ni(1)—O(5)

2.397(14)

88.5(6)

bipyramid

Ni(1)—O(5)

2.397(14)

O(5)—Ni(1)—O(5)

97.7(8)

Ni(1)—O(7)

2.402(13)

O(5)—Ni(1)—O(7)

61.8(5)

125.0(6)

168.9(9)

Ni(1)—O(7)

2.402(13)

81.3(4)

Ni(1)—O(7)

2.597(15)

O(2)—Ni(1)—O(5)

80.4(7)

O(7)—Ni(1)—O(7)

97.5(7)

Ni(1)—O(7)

2.597(15)

127.7(6)

64.3(8)

iii) lattice parameters for β-M x V 2 O 5 materials, wherein M is Ni, Co, Sn, and Pb

Radius

Sample

(Å)

(Å) 18

ζ-V 2 O 5

15.25253(3)

3.602132(4)

10.104167(13)

110.088(0)

521.369(1)

N/A

Ni x V 2 O 5

0.331

15.3711(7)

3.6101(1)

10.0726(5)

109.968(4)

525.335(27)

0.63

Co x V 2 O 5

0.270

15.384

3.6185

10.0893

110.130

527.36

0.67

Sn x V 2 O 5

0.225

15.339(2)

3.6217(3)

10.0781(8)

109.829(7)

526.67(6)

1.22

Pb x V 2 O 5

0.220

15.470(2)

3.6153(4)

10.083(1)

109.396(10)

531.947

1.23.

4. The composition of claim 1 , wherein the M x V 2 O 5 material is selected from the group consisting of nanoparticles, nanowires, nanorods, nanospheres, nanocubes, nanostars, nanosheets, and combinations thereof.

5. The composition of claim 1 , wherein the M x V 2 O 5 material is a nanowire.

6. The composition of claim 1 , wherein the M x V 2 O 5 material is a thin film.

7. The composition of claim 1 , wherein the M x V 2 O 5 material is doped at an oxygen anion site with one element selected from the group consisting of S, Se, Te, P and F.

8. The composition of claim 1 , wherein the quantum dots are cadmium chalcogenide quantum dots, zinc chalcogenide quantum dots, cadmium/zinc chalcogenide quantum dots, or combinations thereof.

9. The composition of claim 1 , wherein the quantum-confined thin film is a cadmium chalcogenide, zinc chalcogenide, cadmium/zinc chalcogenide, or combinations thereof.

10. The composition of claim 1 , wherein one or more metal cation is intercalated into the M x V 2 O 5 material and the metal cations are selected from the group consisting of copper cations, nickel cations, cobalt cations, zinc cations, tin cations, mercury cations, thallium cations, gallium cations, indium cations, bismuth(III) cations and combinations thereof.

Assignments (4)

ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 5, 2024

From: BANERJEE, SARBAJIT; ANDREWS, JUSTIN L.; CHO, JUNSANG

To: THE TEXAS A&M UNIVERSITY SYSTEM

Reel/Frame 067624/0606 →

ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 5, 2024

From: WATSON, DAVID; SUWANDARATNE, NUWANTHI; SHENG, AARON

To: THE RESEARCH FOUNDATION FOR THE STATE UNIVERSITY OF NEW YORK

Reel/Frame 067624/0837 →

CONFIRMATORY LICENSE Recorded Oct 20, 2023

From: TEXAS A&M UNIVERSITY

To: NATIONAL SCIENCE FOUNDATION