Carbon sorbent-azobenzene hybrids for carbon capture and methods of producing and/or using said hybrids

1 . A carbon-based sorbent configured for improved carbon capture, the carbon-based sorbent comprising:

at least one modified carbon-based sorbent comprising:

mesoporous carbon surfaces configured to improve selective CO 2 adsorption; and

at least one carbonaceous material selected from the group consisting of activated carbon, biomass-derived materials, polymer-based synthetic porous or mesoporous carbon, carbonized carbohydrates, and combinations thereof,

wherein

the mesoporous carbon surfaces comprise one or more in-plane sites having at least one first nitrogen functionality and one or more out-of-plane sites having at least one second nitrogen functionality,

wherein the at least one first nitrogen functionality is a different nitrogen functionality than the at least one second nitrogen functionality,

wherein

the one or more in-plane sites are one or more graphitic-N sites, one or more pyrrolic-N sites, one or more pyridinic-N sites, one or more pyridine-N sites, or a combination thereof, and

wherein the one or more out-of-plane sites are one or more azobenzene-N sites.

2 . The carbon-based sorbent of claim 1 , wherein the one or more in-plane sites are at least one graphitic-N site, at least one pyrrolic-N site, at least one pyridinic-N site, and at least one pyridine-N site.

3 . The carbon-based sorbent of claim 1 , wherein the at least one modified carbon-based sorbent is a carbon sorbent-azobenzene hybrid formed by covalent functionalization of the mesoporous carbon surfaces with an azobenzene-containing diazonium salt via electron transfer diazonium chemistry.

4 . The carbon-based sorbent of claim 3 , wherein the carbon sorbent-azobenzene hybrid is a N-doped-carbon sorbent-azobenzene hybrid.

5 . A method for increasing CO 2 capture potential of the carbon-based sorbent of claim 1 , the method comprising:

covalently functionalizing at least one carbon lattice of the carbon-based sorbent comprising mesoporous carbon surfaces;

incorporating one or more in-plane CO 2 philic groups and one or more out-of-plane CO 2 philic groups into the carbon-based sorbent; and

incorporating one or more out-of-carbon lattice plane nitrogen functionalities into the carbon-based sorbent to produce the at least one modified carbon-based sorbent.

6 . The method of claim 5 , wherein the at least one modified carbon-based sorbent is a carbon sorbent-azobenzene hybrid.

7 . The method of claim 6 , wherein the carbon sorbent-azobenzene hybrid is a N-doped-carbon sorbent-azobenzene hybrid.

8 . The method of claim 5 , wherein the one or more in-plane CO 2 philic groups comprise nitrogen doping groups.

9 . The method of claim 8 , wherein the nitrogen doping groups are one or more graphitic-based groups, one or more pyrrolic-based groups, one or more pyridinic-based groups, one or more pyridine-based sites, or a combination thereof.

10 . The method of claim 8 , wherein the one or more out-of-plane CO 2 philic groups is/are one or more azobenzene-based groups.

11 . The method of claim 5 , wherein the one or more in-plane CO 2 philic groups are at least one graphitic-N group, at least one pyrrolic-N group, at least one pyridinic-N group, and at least one pyridine-N group, and the one or more out-of-plane CO 2 philic groups are one or more azobenzene-N groups.

12 . The method of claim 5 , further comprising:

improving selective CO 2 adsorption by simultaneously activating the one or more in-plane CO 2 philic groups and the one or more out-of-plane CO 2 philic groups.

13 . A method for improving noncovalent interactions of the carbon-based sorbent of claim 1 with CO 2 , N 2 , and H 2 , the method comprising:

providing the modified carbon-based sorbent comprising mesoporous carbon surfaces; and

simultaneously activating one or more in-plane sites and one or more out-of-plane sites of the mesoporous carbon surfaces.

14 . The method of claim 13 , further comprising:

selectively capturing CO 2 with the modified carbon-based sorbent during syngas processing, post-combustion processing, or pre-combustion processing.

15 . The method of claim 13 , wherein the modified carbon-based sorbent is a carbon sorbent-azobenzene hybrid or a N-doped-carbon sorbent-azobenzene hybrid.

16 . The method of claim 13 , wherein the one or more in-plane sites is/are nitrogen doping sites and the one or more out-of-plane sites is/are azobenzene-N sites.

17 . The method of claim 13 , further comprising:

contacting the modified carbon-based sorbent to at least one gaseous stream comprising CO 2 therein.

18 . The carbon-based sorbent of claim 1 , wherein:

the at least one modified carbon-based sorbent is a N-doped-carbon sorbent-azobenzene hybrid formed by covalent functionalization of the mesoporous carbon surfaces with an azobenzene-containing diazonium salt via electron transfer diazonium chemistry;

the one or more in-plane sites are at least one graphitic-N site, at least one pyrrolic-N site, at least one pyridinic-N site, and at least one pyridine-N site;

the carbon-based sorbent exhibits a calculated binding energy for CO 2 interacting with one or more azo bridges of about 13.68 kJ/mol, a calculated binding energy for N 2 interacting with one or more azo bridges of about 7.00 kJ/mol, and a calculated binding energy for H 2 interacting with one or more azo bridges of about 2.93 kJ/mol; and

the carbon-based sorbent is configured for use in a carbon capture, utilization, and storage (CCUS) application selected from the group consisting of post-combustion CO 2 capture from flue gas, pre-combustion CO 2 capture from synthesis gas, CO 2 capture from natural gas extraction, CO 2 capture from gas refineries, CO 2 capture from exhaust gases produced by fossil fuel-fired power generation, and combinations thereof.