Owing to the rich porosity and uniform pore size, metal-organic frameworks (MOFs) offer substantial advantages over other materials for the precise and fast membrane separation. However, achieving ultrathin water-stable MOF membranes remains a great challenge. Here, we first report the successful exfoliation of two-dimensional (2D) monolayer aluminum tetra-(4-carboxyphenyl) porphyrin framework (termed Al-MOF) nanosheets. Ultrathin water-stable Al-MOF membranes are assembled by using the exfoliated nanosheets as building blocks. While achieving a water flux of up to 2.2 mol m−2 hour−1 bar−1, the obtained 2D Al-MOF laminar membranes exhibit rejection rates of nearly 100% on investigated inorganic ions. The simulation results confirm that intrinsic nanopores of the Al-MOF nanosheets domain the ion/water separation, and the vertically aligned aperture channels are the main transport pathways for water molecules.
1 July 2020 in Applied Catalysis B: Environment and Energy
The high demand for hydrogen peroxide (H2O2) has been dominantly supplied by the anthraquinone process for various applications globally, including chemical synthesis and wastewater treatment. However, the centralized manufacturing and intensive energy input and waste output are significant challenges associated with this process. Accordingly, the on-site production of H2O2via electro- and photocatalytic water oxidation and oxygen reduction partially is greener and easier to handle and has recently emerged with extensive research aiming to seek active, selective and stable catalysts. Herein, we review the current status and future perspectives in this field focused on carbon-based catalysts and their hybrids, since they are relatively inexpensive, bio-friendly and flexible for structural modulation. We present state-of-the-art progress, typical strategies for catalyst engineering towards selective and active H2O2 production, discussion on electro- and photochemical mechanisms and H2O2 formation through both reductive and oxidative reaction pathways, and conclude with the key challenges to be overcome. We expect promising developments would be inspired in the near future towards practical decentralized H2O2 production and its direct use.
Bioinspired control of ion transport at the subnanoscale has become a major focus in the fields of nanofluidics and membrane separation. It is fundamentally important to achieve rectifying ion-specific transport in artificial ion channels, but it remains a challenge. Here, we report a previously unidentified metal-organic framework nanochannel (MOF NC) nanofluidic system to achieve unidirectional ultrafast counter-directional transport of alkaline metal ions and proton. This highly effective ion-specific rectifying transport behavior is attributed to two distinct mechanisms for metal ions and proton, elucidated by theoretical simulations. Notably, the MOF NC exhibits ultrafast proton conduction stemming from ultrahigh proton mobility, i.e., 11.3 × 10 −7 m 2 /V·s, and low energy barrier of 0.075 eV in MIL-53-COOH subnanochannels. Furthermore, the MOF NC shows excellent osmotic power–harvesting performance in reverse electrodialysis. This work expects to inspire further research into multifunctional biomimetic ion channels for advanced nanofluidics, biomimetics, and separation applications.
Aromatic - aliphatic hydrocarbon separation is a challenging but important industrial process. Pervaporation membrane technology has the potential for separating these mixtures. We developed an oriented monolayer polyhedral (OMP) membrane that consists of a monolayer of ordered polyhedral particles and is anchored by hyperbranched polymers. It contains a high density of straight, selective nanochannels, enabling the preferential transport of aromatic molecules. Compared with traditional mixed-matrix membranes with random orientations, the OMP membrane improves the pervaporation separation index for aromatic-aliphatic hydrocarbon mixtures with C 6 and C 7 compounds, surpassing the performance of existing membranes by 3 to 10 times. This high performance demonstrates the potential of OMP membranes for hydrocarbon molecular separation and their application in the value-added separation of naphtha feedstocks.