Graphene oxide (GO) nanosheets stacked in parallel with subnanometer channels can exhibit an excellent size‐sieving ability for membrane‐based gas separation. However, gas molecules have to diffuse through the tortuous nanochannels, leading to low permeability. Herein we demonstrate two versatile approaches to modify the GO (before membrane fabrication by vacuum‐filtration) to collectively increase gas permeability, etching using hydrogen peroxide to generate in‐plane nanopores and acidifying using hydrochloric acid. For example, a membrane prepared at a pH of 5.0 using the 4‐h‐etched GO (HGO‐4h) shows He permeability of 5.3 Barrer and He/CH4selectivity of 800, which are 5 times and 1.5 times those of the GO membranes, respectively. Decreasing the pH from 5.0 to 2.0 for HGO‐4h enhances He permeability to 57 Barrer and He/CH4selectivity to 1,800. The HGO‐4h prepared at the pH of 2.0 exhibits separation properties of H2/CO2, H2/N2, He/N2, and He/CH4surpassing their corresponding upper bounds.
Single‐layer graphene containing molecular‐sized in‐plane pores is regarded as a promising membrane material for high‐performance gas separations due to its atomic thickness and low gas transport resistance. However, typical etching‐based pore generation methods cannot decouple pore nucleation and pore growth, resulting in a trade‐off between high areal pore density and high selectivity. In contrast, intrinsic pores in graphene formed during chemical vapor deposition are not created by etching. Therefore, intrinsically porous graphene can exhibit high pore density while maintaining its gas selectivity. In this work, the density of intrinsic graphene pores is systematically controlled for the first time, while appropriate pore sizes for gas sieving are precisely maintained. As a result, single‐layer graphene membranes with the highest H2/CH4separation performances recorded to date (H2permeance > 4000 GPU and H2/CH4selectivity > 2000) are fabricated by manipulating growth temperature, precursor concentration, and non‐covalent decoration of the graphene surface. Moreover, it is identified that nanoscale molecular fouling of the graphene surface during gas separation where graphene pores are partially blocked by hydrocarbon contaminants under experimental conditions, controls both selectivity and temperature dependent permeance. Overall, the direct synthesis of porous single‐layer graphene exploits its tremendous potential as high‐performance gas‐sieving membranes.
more » « less- Award ID(s):
- 1907716
- NSF-PAR ID:
- 10446378
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Materials
- Volume:
- 33
- Issue:
- 44
- ISSN:
- 0935-9648
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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