Reduction catalyst, and chemical reactor, reduction method and reduction product-producing system employing the catalyst

Patent metadata

Field	Value
Publication number	US-10829861-B2
Application number	US-201715690610-A
Country	US
Kind code	B2
Filing date	Aug 30, 2017
Priority date	Jan 25, 2017
Publication date	Nov 10, 2020
Grant date	Nov 10, 2020

Abstract

The present embodiments provide a reduction catalyst realizing high reaction efficiency and a reduction reactor employing the catalyst. The reduction catalyst of the embodiment comprises an electric conductor and an organic layer having organic modifying groups placed on the surface of the conductor. The organic modifying groups have an aromatic ring having two or more nitrogen atoms. The reduction catalyst is used in a reduction reactor, and the reactor is also provided.

First claim

The invention claimed is:

1. A reduction catalyst, comprising:
an electric conductor; and
an organic layer having organic modifying groups placed on the surface of the conductor,
wherein:
the organic modifying groups have a structure represented by the following formula (B):

Z is an imidazole group or a triazole group;
Y is a heteroatom-containing group capable of linking to the electric conductor;
nb is an integer of 0 to 6 inclusive; and
the organic modifying groups have a density of 1×10 12 to 10 15 atoms/cm 2 .

2. The reduction catalyst according to claim 1 , wherein Y is —S—.

3. The reduction catalyst according to claim 1 , wherein the organic modifying groups are derived from organic compounds selected from the group consisting of mercaptoethylimidazole, mercaptopropylimidazole, mercaptobutylimidazole, mercaptohexylimidazole, mercaptotriazole, mercaptoethyltriazole, mercaptopropyltriazole, mercaptobutyltriazole, and mercaptohexyltriazole.

4. The reduction catalyst according to claim 1 , wherein the electric conductor comprises a metal selected from the group consisting of: Au, Ag, Cu, Pt, Pd, Zn, Fe, Ti, Sn, In, Hg, Bi and Ni.

5. The reduction catalyst according to claim 1 , wherein Y is selected from the group consisting of —S—, —S═S— and —N═C═S—.

6. The reduction catalyst according to claim 1 , wherein the organic modifying groups have a density of 1×10 13 to 10 15 atoms/cm 2 .

7. A reduction catalyst, comprising:
an electric conductor; and
an organic layer having organic modifying groups placed on the surface of the conductor,
wherein:
the organic modifying groups have a structure represented by the following formula (A) or (B):

each Ra is independently H or an alkyl group of C 1 to C 4 ;
Z is an aromatic ring having two or more nitrogen atoms which are non-cationic nitrogen atoms;
Y is a heteroatom-containing group capable of linking to the electric conductor;
na is an integer of 1 to 5 inclusive; and
nb is an integer of 0 to 6 inclusive,
wherein:
the electric conductor is in the form of metal fine particles; and
the metal particles are loaded on a spacer layer that is made of an organic material and formed on another electric conductor on a current collector.

8. A reduction catalyst, comprising:
an electric conductor; and
an organic layer having organic modifying groups placed on the surface of the conductor,
wherein:
the organic modifying groups have a structure represented by the following formula (A) or (B):

each Ra is independently H or an alkyl group of C 1 to C 4 ;
Z is an aromatic ring having two or more nitrogen atoms which are non-cationic nitrogen atoms;
Y is a heteroatom-containing group capable of linking to the electric conductor;
na is an integer of 1 to 5 inclusive;
nb is an integer of 0 to 6 inclusive; and
the organic modifying groups have a density of 1×10 12 to 10 15 atoms/cm 2 ; and
wherein the electric conductor comprises a metal oxide selected from the group consisting of Ag 2 O, CuO, Ta 2 O 5 , TiO 2 , ZrO 2 , Al 2 O 3 , SiO 2 , ZnO, ITO, and FTO.

9. A chemical reactor comprising:
an oxidation electrode;
a reduction electrode provided with a reduction catalyst; and
a power supply unit connected to the oxidation electrode and the reduction electrode,
wherein said reduction catalyst comprises:
an electric conductor; and
an organic layer having organic modifying groups placed on the surface of the conductor,
wherein:
the organic modifying groups have a structure represented by the following formula (A) or (B):

each Ra is independently H or an alkyl group of C 1 to C 4 ;
Z is an aromatic ting having two or more nitrogen atoms which are non-cationic nitrogen atoms;
Y is a heteroatom-containing group capable of linking to the electric conductor;
na is an integer of 1 to 5 inclusive; and
nb is an integer of 0 to 6 inclusive.

10. The chemical reactor according to claim 9 , wherein the power supply unit comprises a semiconductor layer in which charge separation is caused by light energy.

11. The chemical reactor according to claim 10 , wherein the semiconductor layer is placed between the oxidation electrode and the reduction electrode.

12. A reduction method, comprising:
contacting an electrolyte solution with a reduction electrode provided with a reduction catalyst comprising an electric conductor and an organic layer having organic modifying groups placed on the surface of the conductor; and then introducing a low molecular weight-carbon compound into the electrolyte solution so as to reduce the low molecular weight-carbon compound by the action of the electrode,
wherein:
the organic modifying groups have a structure represented by the following formula (A) or (B):

each Ra is independently H or an alkyl group of C 1 to C 4 ;
Z is an aromatic ring having two or more nitrogen atoms which are non-cationic nitrogen atoms;
Y is a heteroatom-containing group capable of linking to the electric conductor;
na is an integer of 1 to 5 inclusive;
b is an integer of 0 to 6 inclusive; and
the organic modifying groups have a density of 1×10 12 to 10 15 atoms/cm 2 .

13. The reduction method according to claim 12 , wherein the low molecular weight-carbon compound is selected from the group consisting of carbon dioxide, oxalic acid, and glyoxal.

14. A reduction product-producing system, comprising:
a chemical reactor comprising an oxidation electrolytic bath provided with an oxidation catalyst and a reduction electrolytic bath provided with a reduction catalyst an electric conductor and an organic layer having organic modifying groups placed on the surface of the conductor, so as to produce a reduction product by a reduction reaction of carbon dioxide;
an electrolyte solution supply unit by which an electrolyte solution is supplied to the reduction electrolytic bath;
a carbon dioxide supply unit by which carbon dioxide is dissolved in the electrolyte solution so as to keep the reduction reaction in the reduction electrolytic bath and thereby to increase the concentration of the reduction product in the electrolyte solution; and
a separation unit by which the reduction product is separated from the electrolyte solution where the concentration of the electrolyte is increased by the carbon dioxide supply unit,
wherein:
the organic modifying groups have a structure represented by the following formula (A) or (B):

each Ra is independently H or an alkyl group of C 1 to C 4 ;
Z is an aromatic ring having two or more nitrogen atoms which are non-cationic nitrogen atoms;
Y is a heteroatom-containing group capable of linking to the electric conductor;
na is an integer of 1 to 5 inclusive;
nb is an integer of 0 to 6 inclusive; and
the organi

Assignees

• Toshiba Kk

Inventors

• Tamura Jun
• Mikoshiba Satoshi
• Kudo Yuki
• Ono Akihiko
• Kitagawa Ryota
• Yamagiwa Masakazu
• Sugano Yoshitsune

Classifications

• C25B9/19

  with diaphragms · CPC title

• C25B3/25

  Reduction · CPC title

• C25B1/55

  Photoelectrolysis · CPC title

• C25B11/095

  at least one of the compounds being organic · CPC title

• C25B9/00 Primary

  Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features · CPC title