Advanced Functional Hierarchical Nanoporous Structures with Tunable Microporous Coatings Formed via an Interfacial Reaction Processing.

It is challenging, but constructing hierarchical nanoporous structures with microporous coatings for various important applications, such as entrapment of homogeneous catalysts, size/shape selective catalysis, and so forth, is an urgent need. Moreover, microporous inorganic coatings are particularly desirable because of their excellent stability in organic solvents and at elevated temperatures and pressures. In this study, we design a novel liquid phase interfacial reaction process to form a defect-free, hybrid coating, which can be subsequently converted into microporous coatings, with tunable pore size, on nanoporous materials. As an example to entrap functional materials, tetrakis(triphenylphosphine) palladium (Pd(PPh3)4) was in situ synthesized in the mesoporous channels and encapsulated by the microporous coating shell. The encapsulated Pd(PPh3)4 catalyst exhibited negligible Pd leaching, providing a promising solution for the challenging catalyst separation problem in homogeneous catalysis. These results suggest that this novel strategy might be an effective way of forming microporous inorganic coatings on nanoporous materials for entrapping functional materials for wide applications.

Molecular Layer Deposition-Modified 5A Zeolite for Highly Efficient CO2 Capture.

Effective pore mouth size of 5A zeolite was engineered by depositing an ultrathin layer of microporous TiO2 on its external surface and appropriate pore misalignment at the interface. As a result, a slightly bigger N2 molecule (kinetic diameter: 0.364 nm) was effectively excluded, whereas CO2 (kinetic diameter: 0.33 nm) adsorption was only influenced slightly. The prepared composite zeolite sorbents showed an ideal CO2/N2 adsorption selectivity as high as ∼70, a 4-fold increase over uncoated zeolite sorbents, while maintaining a high CO2 adsorption capacity (1.62 mmol/g at 0.5 bar and 25 °C) and a fast CO2 adsorption rate.

Ultrathin graphene oxide-based hollow fiber membranes with brush-like CO2-philic agent for highly efficient CO2 capture.

Among the current CO2 capture technologies, membrane gas separation has many inherent advantages over other conventional techniques. However, fabricating gas separation membranes with both high CO2 permeance and high CO2/N2 selectivity, especially under wet conditions, is a challenge. In this study, sub-20-nm thick, layered graphene oxide (GO)-based hollow fiber membranes with grafted, brush-like CO2-philic agent alternating between GO layers are prepared by a facile coating process for highly efficient CO2/N2 separation under wet conditions. Piperazine, as an effective CO2-philic agent, is introduced as a carrier-brush into the GO nanochannels with chemical bonding. The membrane exhibits excellent separation performance under simulated flue gas conditions with CO2 permeance of 1,020 GPU and CO2/N2 selectivity as high as 680, demonstrating its potential for CO2 capture from flue gas. We expect this GO-based membrane structure combined with the facile coating process to facilitate the development of ultrathin GO-based membranes for CO2 capture.

Self-Assembly: A Facile Way of Forming Ultrathin, High-Performance Graphene Oxide Membranes for Water Purification.

Single-layer graphene oxide (SLGO) is emerging as a new-generation membrane material for high-flux, high-selectivity water purification, owing to its favorable two-dimensional morphology that allows facile fabrication of ultrathin membranes with subnanometer interlayer channels. However, reliable and precise molecular sieving performance still necessarily depends on thick graphene oxide (GO) deposition that usually leads to low water flux. This trade-off between selectivity and flux significantly impedes the development of ultrathin GO membranes. In this work, we demonstrate that the selectivity/flux trade-off can be broken by self-assembly of SLGO via simple deposition rate control. We find GO membranes, prepared by slow deposition of SLGO flakes, exhibit considerably improved salt rejection, while counterintuitively having 2.5-4 times higher water flux than that of membranes prepared by fast deposition. This finding has extensive implications of designing/tuning interlayer nanostructure of ultrathin GO membranes by simply controlling SLGO deposition rate and thus may greatly facilitate their development for high flux, high selectivity water purification.

Ultrafast Nanofiltration through Large-Area Single-Layered Graphene Membranes.

Perforated single-layered graphene has demonstrated selectivity and flux that is orders of magnitude greater than state-of-the-art polymer membranes. However, only individual graphene sheets with sizes up to tens of micrometers have been successfully fabricated for pressurized permeation studies. Scaling-up and reinforcement of these atomic membranes with minimum cracks and pinholes remains a major hurdle for practical applications. We develop a large-area in situ, phase-inversion casting technique to create 63 cm2 high-quality single-layered perforated graphene membranes for ultrafast nanofiltration that can operate at pressures up to 50 bar. This result demonstrates the feasibility of our technique for creating robust large-area, high quality, single-layered graphene and its potential use as a pressurized nanofiltration membrane.

Continuously Adjustable, Molecular-Sieving "Gate" on 5A Zeolite for Distinguishing Small Organic Molecules by Size.

Zeolites/molecular sieves with uniform, molecular-sized pores are important for many adsorption-based separation processes. Pore size gaps, however, exist in the current zeolite family. This leads to a great challenge of separating molecules with size differences at ~0.01 nm level. Here, we report a novel concept, pore misalignment, to form a continuously adjustable, molecular-sieving "gate" at the 5A zeolite pore entrance without sacrificing the internal capacity. Misalignment of the micropores of the alumina coating with the 5A zeolite pores was related with and facilely adjusted by the coating thickness. For the first time, organic molecules with sub-0.01 nm size differences were effectively distinguished via appropriate misalignment. This novel concept may have great potential to fill the pore size gaps of the zeolite family and realize size-selective adsorption separation.

Tuning the underwater oleophobicity of graphene oxide coatings via UV irradiation.

Ultraviolet (UV) irradiation was utilized to gradually modify the chemistry and structure of graphene oxide (GO) flakes, as confirmed by XPS and AFM. Ultrathin GO coatings/membranes, made of UV-irradiated flakes, showed tunable underwater oleophobicity. UV-treated, superoleophobic GO membranes exhibited excellent antifouling capability for oil/water separation.