# US 2022/0033259 A1 · Catalysed process of production of hydrogen from silylated derivatives as hydrogen carrier compounds

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- Number: US 2022/0033259 A1
- Document ID: US20220033259A1
- Status: Published application
- Kind: A1
- Application number: 17/309,049
- Filed: 2019-10-31
- Published: 2022-02-03
- Earliest claimed: 2018-11-28
- Assignees: Hysilabs, SAS
- Applicants: Hysilabs, SAS
- Inventors: Benjamin BURCHER; Vincent LOME; Remy BENOIT
- Web page: https://patentgrep.com/patent/US20220033259A1

## CPC

- C01B 3/065: by reaction of inorganic compounds with hydrides
- C08G 77/12: containing silicon bound to hydrogen
- C08L 83/04: Polysiloxanes
- C01B 2203/1041: Composition of the catalyst
- Y02E 60/36: Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

The present invention relates to a catalysed process of production of hydrogen from silylated derivatives as hydrogen carrier compounds. The present invention also relates to a new catalyst used in the catalysed process of production of hydrogen from silylated derivatives as hydrogen carrier compounds.

## Claims

### Claim 1

Method for producing hydrogen comprising the steps consisting in contacting a hydrogen carrier compound (C) comprising one or more Si—H bonds with a hydrogen release catalyst Y and an optional hydrogen release catalyst X wherein the hydrogen release catalyst Y is selected from formula
wherein Y is O or S, and
X1, X2, are each independently selected from halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR3, SiR6R7R8, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups
Or
X1 and X2=—CRaRb form together with the carbon atom to which they are attached a 3 to 10-membered cycloalkyl, optionally substituted by one to three R9 groups and Ra, Rb are each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups
Or
X1 and X2=NRaRb with Ra and Rb, each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups
Or
X1 is selected from halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR3, SiR6R7R8 and X2=NRaRb with Ra and Rb, each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups
Or
X1 and X2=NRc form together with the carbon atom to which they are attached a 3 to 10-membered heterocycloalkyl, optionally substituted by one to three R9 groups and Rc is selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups
Or
X1=—CRaRb with Ra, Rb are each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10 and X2=NRc form together with the carbon atom to which they are attached a 3 to 10-membered heterocycloalkyl, optionally substituted by one to three R9 groups with Rc selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups
wherein
R3 is H, C1-C6 alkyl, C6-C10 aryl, C6-C12 aralkyl;
R6, R7, R8 are each independently selected from H, OR3, C1-C6 alkyl, C6-C10 aryl, C6-C12 aralkyl;
R9 is selected from halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, NO2, NR11R12, CN, C(═O)R10, C(═O)OR10, S(═O)CH3, wherein said alkyl and aryl groups are optionally substituted by one or more halogen or C1-C10 alkyl or OR3;
R10 is H, C1-C6 alkyl, C6-C10 aryl, C6-C12 aralkyl; and
R11, R12 are each independently selected from H, or C1-C10 alkyl, and
wherein the ratio between the sum of the moles of hydrogen release catalyst Y and the moles of the optional hydrogen release catalyst X relative to the moles of the hydrogen carrier compound (C) multiplied by the number of [Si—H] bonds of compound (C) is inferior or equal to 0.3, and/or wherein the ratio between the sum of the mass of hydrogen release catalyst Y and the mass of the optional hydrogen release catalyst X relative to the mass of the hydrogen carrier compound (C) is inferior or equal to 0.2.

### Claim 2 (depends on 1)

Method for producing hydrogen according to claim 1 wherein the ratio between the sum of the moles of hydrogen release catalyst Y and the moles of the optional hydrogen release catalyst X relative to the moles of the hydrogen carrier compound (C) multiplied by the number of [Si—H] bonds of compound (C) ranges from 0.005 to 0.3, and/or
wherein the ratio between the sum of the mass of hydrogen release catalyst Y and the mass of the optional hydrogen release catalyst X relative to the mass of the hydrogen carrier compound (C) is comprised between 0.01 and 0.2.

### Claim 3 (depends on 1)

Method for producing hydrogen according to claim 1, wherein the ratio between the sum of the moles of hydrogen release catalyst Y and the moles of the optional hydrogen release catalyst X relative to the moles of the hydrogen carrier compound (C) multiplied by the number of [Si—H] bonds of compound (C) ranges from 0.01 to 0.1, and/or wherein the ratio between the sum of the mass of hydrogen release catalyst Y and the mass of the optional hydrogen release catalyst X relative to the mass of the hydrogen carrier compound (C) is comprised between 0.02 and 0.07.

### Claim 4 (depends on 1)

Method for producing hydrogen according to claim 1, wherein the compound (C) comprises one or more monomer unit of formulae:
wherein
R is a bond, C1-C6 alkylene or (C1-C4 alkylene)q-Z-(C1-C4 alkylene)r;
Z is O, NR10, S(O)y, CR10═CR10, C≡C, C6-C10 arylene, 5-10 membered heteroarylene, or C3-C6 cycloalkylene;
R1, R2 are each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, aralkyl, 5 to 10-membered heteroaryl, OR3, NR4R5, SiR6R7R8, wherein said aryl groups are optionally substituted by one to three R9 groups;
R1′, R2′ are each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, aralkyl, 5 to 10-membered heteroaryl, OR3, NR4R5, SiR6R7R8, wherein said aryl groups are optionally substituted by one to three R9 groups;
R3 is H, C1-C6 alkyl, C6-C10 aryl, C6-C12 aralkyl;
R4, R5 are each independently selected from H, C1-C6 alkyl, C6-C10 aryl, C6-C12 aralkyl;
R6, R7, R8 are each independently selected from H, OR3, C1-C6 alkyl, C6-C10 aryl, C6-C12 aralkyl, SiH3;
R9 is selected from halogen, C1-C10 alkyl, OR10, NO2, NR11R12, CN, C(═O)R10, C(═O)OR10, S(═O)CH3, wherein said alkyl group is optionally substituted by one or more halogen;
R10 is H, or C1-C3 alkyl;
R11, R12 are each independently selected from H, or C1-C10 alkyl;
q, r are 0 or 1;
y is 0, 1 or 2;
m, n and p are integers representing the number of repeating units, with n being superior or equal to 1, p being 0 or 1 and m being 0 or 1;
A, B are each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR3, OSiR6R7R8, NR4R5, SiR6R7R8, CR13R14R15 wherein s aid aryl groups are optionally substituted by one to three R9 groups; and
R13, R14, R15 are each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR3, NR4R5, SiR6R7R8; and
wherein the compound (C) comprises at least one group Si—H.

### Claim 5 (depends on 4)

Method for producing hydrogen according to claim 4 wherein, in the compound (C) formulae,
p=0 and m=1; and/or
R1=Me or H; and/or
R1 is Me and n is superior to 1 and inferior to 15 000; preferably inferior to 1000; for example between 20 and 500.

### Claim 6 (depends on 4)

Method for producing hydrogen according to claim 4 wherein compound (C) is Polyhydromethylsiloxane.

### Claim 7 (depends on 4)

Method for producing hydrogen according to claim 4, wherein the compound (C) comprises one or more monomer unit of formulae
wherein R1 is H and n is superior to 1.

### Claim 8 (depends on 4)

Method for producing hydrogen according to claim 4 wherein, in the compound (C) formulae, A═SiMe3, Me or SiH3 and B═OMe, OSiMe3 or OSiH3.

### Claim 9 (depends on 4)

Method for producing hydrogen according to claim 4 wherein, the compound (C) comprises one or more monomer unit of formula
wherein n is comprised between 1 and 30, preferably between 2 and 20.

### Claim 10

Method for producing hydrogen comprising the steps consisting in contacting a hydrogen carrier compound (C) comprising one or more Si—H bonds with a hydrogen release catalyst Y and an optional hydrogen release catalyst X wherein the hydrogen release catalyst Y is selected from formula
wherein Y is O or S, and
X1, X2, are each independently selected from halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR3, SiR6R7R8, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups
Or
X1 and X2=—CRaRb form together with the carbon atom to which they are attached a 3 to 10-membered cycloalkyl, optionally substituted by one to three R9 groups and Ra, Rb are each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups
Or
X1 and X2=NRaRb with Ra and Rb, each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups
Or
X1 is selected from halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR3, SiR6R7R8 and X2=NRaRb with Ra and Rb, each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups
Or
X1 and X2=NRc form together with the carbon atom to which they are attached a 3 to 10-membered heterocycloalkyl, optionally substituted by one to three R9 groups and Rc is selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups
Or
X1=—CRaRb with Ra, Rb are each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10 and X2=NRc form together with the carbon atom to which they are attached a 3 to 10-membered heterocycloalkyl, optionally substituted by one to three R9 groups with Rc selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups
wherein
R3 is H, C1-C6 alkyl, C6-C10 aryl, C6-C12 aralkyl;
R6, R7, R8 are each independently selected from H, OR3, C1-C6 alkyl, C6-C10 aryl, C6-C12 aralkyl;
R9 is selected from halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, NO2, NR11R12, CN, C(═O)R10, C(═O)OR10, S(═O)CH3, wherein said alkyl and aryl groups are optionally substituted by one or more halogen or C1-C10 alkyl or OR3;
R10 is H, C1-C6 alkyl, C6-C10 aryl, C6-C12 aralkyl; and
R11, R12 are each independently selected from H, or C1-C10 alkyl, and
wherein the hydrogen carrier compounds (C) is selected amongst siloxane hydrogen carrier compounds comprising one or more units of formula (I):
wherein n is an integer superior or equal to 3 and inferior or equal to 500, and
wherein the molar ratio of the sum of the {claimed catalyst Y and catalyst X} relative to the [SiOH2] monomer units in compound (C) is lower than or equal to 0.6.

### Claim 11 (depends on 10)

Method for producing hydrogen according to claim 10 wherein the molar ratio of the sum of the {claimed catalyst Y and catalyst X} relative to the [SiOH2] monomer units in compound (C) ranges from 0.01 to 0.5.

### Claim 12 (depends on 10)

Method for producing hydrogen according to claim 10, wherein Y is O in the catalyst formula.

### Claim 13 (depends on 10)

Method for producing hydrogen according to claim 10, wherein X1 is —NRaRb in the catalyst formula.

### Claim 14 (depends on 10)

Method for producing hydrogen according to claim 10, wherein X1 and X2 are both selected from —NRaRb in the catalyst formula.

### Claim 15 (depends on 10)

Method for producing hydrogen according to claim 10, wherein the catalyst is selected from 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (DMPU), tetramethylurea, urea, N,N-dimethylacetamide, cyclohexanone, or mixtures thereof.

### Claim 16 (depends on 10)

Method for producing hydrogen according to claim 10, wherein the catalyst is supported.

### Claim 17 (depends on 10)

Method for producing hydrogen according to claim 10, wherein the compound (C) comprises one or more monomer unit of formulae
wherein n is inferior to 500.

### Claim 18 (depends on 10)

Method for producing hydrogen according to claim 10, wherein the compound (C) is
wherein n is an integer superior or equal to one and inferior or equal to 32.

### Claim 19 (depends on 10)

Method for producing hydrogen according to claim 10, wherein the step of contacting the hydrogen carrier compound (C) with the claimed hydrogen release catalyst Y is performed in the absence of catalyst X.

### Claim 20 (depends on 1)

Hydrogen release catalyst Y, which can be used in the method for producing hydrogen according to claim 1, wherein said catalyst Y is selected from formula
Wherein Y is O or S, and
X1, X2, are each independently selected from halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR3, SiR6R7R8, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups
Or
X1 and X2=—CRaRb form together with the carbon atom to which they are attached a 3 to 10-membered cycloalkyl, optionally substituted by one to three R9 groups and Ra, Rb are each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups
Or
X1 and X2=NRaRb with Ra and Rb, each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups
Or
X1 is selected from halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR3, SiR6R7R8 and X2=NRaRb with Ra and Rb, each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups
Or
X1 and X2=NRc form together with the carbon atom to which they are attached a 3 to 10-membered heterocycloalkyl, optionally substituted by one to three R9 groups and Rc is selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups
Or
X1=—CRaRb with Ra, Rb are each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10 and X2=NRc form together with the carbon atom to which they are attached a 3 to 10-membered heterocycloalkyl, optionally substituted by one to three R9 groups with Rc selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups
wherein
R3 is H, C1-C6 alkyl, C6-C10 aryl, C6-C12 aralkyl;
R6, R7, R8 are each independently selected from H, OR3, C1-C6 alkyl, C6-C10 aryl, C6-C12 aralkyl;
R9 is selected from halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10 membered heteroaryl, OR10, NO2, NR11R12, CN, C(═O)R10, C(═O)OR10, S(═O)CH3, wherein said alkyl and aryl groups are optionally substituted by one or more halogen or C1-C10 alkyl or OR3;
R10 is H, C1-C6 alkyl, C6-C10 aryl, C6-C12 aralkyl; and
R11, R12 are each independently selected from H, or C1-C10 alkyl.

### Claim 21 (depends on 1)

Hydrogen release catalyst Y which can be used in the method for producing hydrogen according to claim 1, wherein said catalyst Y is selected from formula
Wherein Y is O or S, and
X1, X2, are each independently selected from halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR3, SiR6R7R8, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups
Or
X1 and X2=—CRaRb form together with the carbon atom to which they are attached a 3 to 10-membered cycloalkyl, optionally substituted by one to three R9 groups and Ra, Rb are each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups
Or
X1 and X2=NRaRb with Ra and Rb, each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups
Or
X1 is selected from halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR3, SiR6R7R8 and X2=NRaRb with Ra and Rb, each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups
Or
X1 and X2=NRc form together with the carbon atom to which they are attached a 3 to 10-membered heterocycloalkyl, optionally substituted by one to three R9 groups and Rc is selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups
Or
X1=—CRaRb with Ra, Rb are each independently selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10 and X2=NRc form together with the carbon atom to which they are attached a 3 to 10-membered heterocycloalkyl, optionally substituted by one to three R9 groups with Rc selected from H, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, aralkyl, 5 to 10-membered heteroaryl, OR10, wherein said alkyl and aryl groups are optionally substituted by one to three R9 groups
wherein
R3 is H, C1-C6 alkyl, C6-C10 aryl, C6-C12 aralkyl;
R6, R7, R8 are each independently selected from H, OR3, C1-C6 alkyl, C6-C10 aryl, C6-C12 aralkyl;
R9 is selected from halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aralkyl, 5 to 10-membered heteroaryl, OR10, NO2, NR11R12, CN, C(═O)R10, C(═O)OR10, S(═O)CH3, wherein said alkyl and aryl groups are optionally substituted by one or more halogen or C1-C10 alkyl or OR3;
R10 is H, C1-C6 alkyl, C6-C10 aryl, C6-C12 aralkyl; and
R11, R12 are each independently selected from H, or C1-C10 alkyl wherein the catalyst Y is a Si—H bond cleavage catalyst.