Biomimetic Sorbents for Selective CO2 Capture Investigators

Nitrogen-doped hierarchical mesoporous carbon is synthesized via molecular coassembly and polymerization of a rationally designed pyrrole derivative via softtemplating with a triblock copolymer in solution, followed by mild carbonization at 350 C and chemical activation at 500 C. The nitrogen-rich porous carbon possesses 5.8 wt% N and has a high surface area of 942 m g with hierarchically distributed pore sizes ranging from sub-nanometer to micrometer. It shows excellent CO2/N2 separation properties, including high CO2 capacity (at 298 K, 1.4 and 4.5 mmol g , 0.1 and 1 bar, respectively), record-high CO2/N2 selectivity (331:1 at 298 K), mild regeneration conditions, and multi-cycle stability under different operating conditions. These properties suggest its significant potential as an efficient CO2 sorbent. Furthermore, our design strategy provides a promising approach for the synthesis of other polymeric-based porous materials. In addition, we have investigated the thermodynamics of CO2 adsorption/desorption for a set of diamine functionalized SBA-15 sorbents under simulated flue gas conditions (0.15 bar CO2, 313 K). Enthalpies of CO2 adsorption (ΔH°ads) of -21.7 and -21.0 kcal mol were obtained for primary diamine (1°-SBA) and secondary diamine (2°-SBA) functionalized material, respectively. Equilibrium constants and ΔG°ads values were estimated using a simple Langmuir adsorption model. Combining ΔG°ads and ΔH°ads values provides a complete thermodynamic picture for the adsorption process. Introduction Global annual energy-related CO2 emissions reached a record high of 31.2 gigatonnes (Gt) in 2012[1], and are expected to rise continuously given the growing energy demands and widespread reliance on fossil fuel energy infrastructure. The mitigation of CO2 emission has been recognized as a crucial necessity, as CO2 is a major contributing greenhouse gas correlated to the negative effects of global warming, including sea level rise, significant variation in weather patterns, and threats to human health and wildlife habitats[2]. This has motivated research of post-combustion CO2 capture and storage (CCS) technologies, targeted at large point source emitters of CO2 such as coal fired power plants. Absorption with aqueous solutions of amines remains the benchmark approach at scale, but wide spread implementation is currently prohibited by the high energetic cost of sorbent regeneration, chiefly due to water vaporization. Translation of nitrogen based sorbents to porous solid supports is therefore an ongoing area of research. Background Carbon Capture The state-of-the-art technology for CO2 capture, aqueous amine scrubbing[3], has yet to be proven practical at scale due to considerable energy penalties of regeneration (ca. 50 kcal mol) [4], chiefly due to the vaporization of liquid water [5-8]. Solid-state postcombustion CO2 sorbents have certain advantages over traditional aqueous amine systems, such as relatively low regeneration energy requirements [8, 9], tunable pore morphology [10-13], and chemical variability through heteroatom doping or surface functionalization[14]. A variety of materials have been investigated for CO2 capture, including zeolites, metal-organic frameworks (MOFs), porous carbons, porous silicas, and porous polymers[9, 15-20]. Nevertheless, it remains a significant challenge to achieve scalable sorbents that meet all of the requirements for CO2 capture, i.e., fast kinetics, high CO2 capacity and selectivity, mild regeneration conditions, and multicycle stability. For example, while chemisorbents like porous solid-supported amines may achieve excellent equilibrium adsorption capacities and CO2/N2 selectivities through chemical reactions with CO2[9, 21, 22], materials often require relatively high regeneration temperatures and long adsorption/desorption cycle times[9]. On the other hand, typical physisorbents, such as activated carbons and MOFs, can be regenerated with minimal energy input, yet have relatively low capacities under post-combustion conditions because of weak CO2-sorbent interactions and competing adsorption of other flue gas components, like N2 and H2O[8, 9] Nitrogen-Doped Porous Carbon Materials Ordered N-doped mesoporous carbons have attracted considerable attention in the application of CO2 capture owing to their high surface area, tunable pore structure, narrow pore size distribution, high N weight percentages, and mechanical, thermal, and electric properties. Typically, N-doped mesoporous carbons are prepared by a nanocasting method using a sacrificial template like porous silica. Nitrogen functionality can be incorporated by impregnation with nitrogen-containing organic molecules, followed by carbonization and removal of the silica template, or through post-synthesis treatment of mesoporous carbon using acetonitrile or ammonia chemical vapor deposition. These multiple-step processes are costly and time consuming. Other methods include the co-assembly of a nitrogen-containing monomer, melamine resin, urea-phenolformaldehyde resin, or dicyandiamide with a structural directing agent; however, the resulting porous polymers usually exhibit poor thermal stability. The decomposition process is further promoted by the high oxygen content within the triblock polymer. Development of reliable and facile strategies to synthesize N-doped mesoporous carbons without the use of a hard template is highly desirable. Carbons made by carbonization of polypyrrole possess graphitic structures and have high thermal conductivity that is desirable for heat transfer during adsorption and/or thermal regeneration. In this work, we report the successful synthesis of nitrogen-doped porous carbon using a modified-pyrrole monomer as the nitrogen source, which displays high CO2 capacity, high CO2/N2 selectivity, and facile regeneration. CO2 Sorption Thermodynamics A diverse range of solid CO2 sorbents have been studied, but emphasis is typically placed on maximizing the equilibrium CO2 capacities of materials. The thermodynamics of the adsorption/desorption process and, specifically, how the structure of sorbent molecules dictate the freeenergy of both CO2 adsorption and desorption reactions are not well understood. Mesoporous silicas are attractive solid supports due to their high surface areas, well-defined molecular-scale pore structures, and established synthetic and covalent modification procedures. By chemically altering the structure of amine sorbents and incorporating said sorbents onto the surface of ordered mesoporous silica, we have gained chemical level insights about the CO2 capture process and how amine structural perturbation effects the thermodynamics of the adsorption process (Scheme 1). Scheme 1. Changes to reaction free-energy with amine structural perturbation. Results Nitrogen-Doped Mesoporous Carbon A series of N-doped mesoporous activated carbons (SU-MAC-500, 600 and 800) have been synthesized, with surface areas ranging from 942 to 2369 m g, abundant ultrasmall microporosity (Figure 1), and various types of nitrogen functionalities (Figure 2). CO2 sorption capacity measurements were performed by pure gas adsorption, yielding values as high as 1.4 mmol g and 4.5 mmol g at 0.1 and 1 bar CO2, respectively (298 K) (Figure 3). More importantly, the N-doped carbons show unprecedented CO2/N2 selectivity of 331:1 at 298 K. Figure 1: Cumulative pore volumes and pore size distributions (PSDs, inset) based upon the CO2 adsorption isotherms at 273 K. Figure 2: (a) Schematic of proposed nitrogen functionalities in SU-MAC materials, including N5, N-6, N-Q and N-oxides and (b) N1s X-ray photoelectron spectra (XPS) of SU-MAC materials (398.1 eV: N-6, 400.0 eV: N-5, 403.4 eV: N-oxide). Figure 3: Gas adsorption performance of SU-MAC-500: CO2 at 273 K, 298 K and 323 K, and N2 at 298 K 0 0.2 0.4 0.6 0.1 1 C u m u la ti v e V ( c m 3 g -1 ) Pore Diameter, d (nm) SU-MAC-500