Preserving Macroporosity in Type III Porous Liquids.

Preserving large permanent pore structures in a fluid may endow conventional liquids with emergent physical properties. However, such materials are challenging to make because of the tendency of the pores to be filled and occupied by the solvent molecules. Here, we report the design and synthesis of the first Type III porous liquid (PL) containing uniform yet stable 480 nm cavities. This was achieved by first constructing a single crystalline hollow metal-organic framework (MOF), UiO-66-NH2 , through chemical etching. The thin yet defect-free MOF shell effectively excludes the bulky poly(dimethylsiloxane) solvent molecules from entering the cavity through its 4 Šaperture, resulting in the preservation of both micro- and macroporosity in the PL. These enormous void spaces allow the PL to reversibly host and release up to 27 wt % water for up to 10 cycles. The switching between the "dry" state and the "wet" state led to a large changes of the thermal conductivity of the PL from 0.140 to 0.256 W m-1 K-1 , affording a guest-responsive liquid thermal switch with a switching ratio of 1.8.

Facile One-Step Metal-Organic Framework Surface Polymerization Method.

A simple one-step approach that only uses commercially available small-molecule reagents was developed for the construction of metal-organic framework (MOF)@polymer core-shell composite particles. Here, the MOF particles were incorporated into a typical reversible addition-fragmentation chain-transfer (RAFT) polymerization solution containing a solvent, a chain-transfer agent, an initiator, and a monomer mixture with at least one hydrogen-bond-donating monomer such as 2-hydroxyethyl methacrylate or acrylic acid. The elongation of polymer chains during polymerization gradually increases MOF/polymer interfacial interaction and eventually results in the adsorption of a random copolymer onto the MOF surface through hydrogen-bond cross-linking and MOF/polymer interfacial interaction. The continuous growth of the polymer leads to a uniform polymer coating on the MOF. Benefiting from the tacky polymer surface, these well-defined MOF@polymer composite particles can be further assembled into highly ordered monolayer composite thin films either alone or with an additional polymer matrix through the Langmuir-Blodgett technique.

A Physical Entangling Strategy for Simultaneous Interior and Exterior Modification of Metal-Organic Framework with Polymers.

A new strategy uses a common feature of metal-organic frameworks (MOFs), namely porosity rather than functionality, to achieve simultaneous interior and exterior modification of a MOF with polymers. We demonstrate that an anhydride-terminated polyimide oligomer can be covalently grafted to the amine-functionalized methacrylate polymer backbone residing underneath the MOF surface and physically entangled within the 3D nanochannels. The MOF particles were evenly coated with a thin layer of polyimide brushes on the surface thereby exhibiting increased dispersibility in solvent media as well as in polymer matrix. The MOF pores were decorated with aliphatic amine groups to endow the MOF with higher CO2 affinity at low pressure. The polyimide-grafted surface allowed MOF particles to interact favorably with the polyimide matrix, producing defect-free MMM with drastically improved CO2 permeability and maintaining the inherent CO2 /N2 and CO2 /CH4 selectivity of the neat polymeric membrane.

Wave-turbulence interaction-induced vertical mixing and its effects in ocean and climate models.

Heated from above, the oceans are stably stratified. Therefore, the performance of general ocean circulation models and climate studies through coupled atmosphere-ocean models depends critically on vertical mixing of energy and momentum in the water column. Many of the traditional general circulation models are based on total kinetic energy (TKE), in which the roles of waves are averaged out. Although theoretical calculations suggest that waves could greatly enhance coexisting turbulence, no field measurements on turbulence have ever validated this mechanism directly. To address this problem, a specially designed field experiment has been conducted. The experimental results indicate that the wave-turbulence interaction-induced enhancement of the background turbulence is indeed the predominant mechanism for turbulence generation and enhancement. Based on this understanding, we propose a new parametrization for vertical mixing as an additive part to the traditional TKE approach. This new result reconfirmed the past theoretical model that had been tested and validated in numerical model experiments and field observations. It firmly establishes the critical role of wave-turbulence interaction effects in both general ocean circulation models and atmosphere-ocean coupled models, which could greatly improve the understanding of the sea surface temperature and water column properties distributions, and hence model-based climate forecasting capability.

Silk nanofibrils-MOF composite membranes for pollutant removal from water.

Membrane separation technology is considered an effective strategy to remove pollutants in sewage. However, it remains a significant challenge to fabricate inexpensive membranes with high purification efficiency. Therefore, the present study proposes the integration of silk nanofibrils (SNFs) and polydopamine⊂metal-organic framework (PDA⊂MOF) nanoparticles to prepare self-supporting membranes, which can effectively intercept nanoparticle pollutants through the size exclusion effect and can strongly adsorb organic dyes and metal ions by SNF. In addition, PDA⊂MOF enables these membranes to adsorb small molecules and heavy metal ions during the filtration process, thereby effectively removing various pollutants from sewage. The integration of size-exclusion and adsorption capabilities enables the SNF/PDA⊂MOF membrane to remove nanoparticles, small-molecule dyes, heavy metal ions, and radioactive elements. This work provides a rational approach for the design and development of the next generation of water treatment membranes and is expected to be used in environmental, food-related, and biomedical fields.

Atmospheric microplastics in the Northwestern Pacific Ocean: Distribution, source, and deposition.

Microplastic pollution is recognized as a ubiquitous global issue. However, limited information is available concerning microplastics in the marine air. Here we present the occurrence and distribution of atmospheric microplastics in the Northwestern Pacific Ocean, with abundance ranging from 0.0046 to 0.064 items/m3. The microplastics were in various shapes and polymer types, of which fibrous rayon (67%) and polyethylene terephthalate (PET, 23%) accounted for the majority. The atmospheric microplastics in the pelagic area showed higher abundance and smaller size compared to those in the nearshore area, indicating smaller-sized microplastics in the atmosphere might travel long distances over the ocean. The atmospheric microplastic distribution was not only affected by weather conditions but might also be related to the microplastic sources. The microplastic polymer types combined with the backward trajectory model analysis showed that atmospheric microplastics in the Northwestern Pacific Ocean mainly originated from the land and the adjacent oceanic atmosphere. Spearman's correlation coefficient of the relationship between the features of microplastics in the atmosphere and surface seawater tended to increase with increasing offshore distances. Our field-based research revealed that atmospheric microplastics were a non-negligible source of marine microplastic pollution.

Two-dimensional Zr/Hf-hydroxamate metal-organic frameworks.

Novel two-dimensional kagome metal-organic frameworks with mononuclear Zr4+/Hf4+ nodes chelated by benzene-1,4-dihydroxamate linkers were synthesized. The MOFs, namely SUM-1, are chemically robust and kinetically favorable, as confirmed by theoretical and experimental studies. SUM-1(Zr) can be readily made into large (∼100 µm) single crystals and nanoplates (∼50 nm), constituting a versatile MOF platform.

Anisotropy of the sea surface height wavenumber spectrum from altimeter observations.

In this paper, the zonal and meridional sea surface height (SSH) wavenumber spectra are systematically calculated using along-track and gridded altimeter products, and the slopes of the SSH wavenumber spectra over the mesoscale band, which is defined by the characteristic length scale of mesoscale signals, are estimated. The results show that the homogeneous spectral slopes calculated from the along-track and gridded altimeter datasets have a similar spatial pattern, but the spectral slopes from gridded altimeter data are generally steeper than that from the along-track data with an averaged difference of 1.5. Significant differences are found between the zonal and meridional spectra, which suggest that SSH wavenumber spectra are indeed anisotropic. Furthermore, the anisotropy exhibits strong regional contrast: in the equatorial region, the zonal spectrum is steeper than its corresponding meridional spectrum, while in the eastward-flowing high EKE regions the meridional spectrum is steeper than its zonal counterpart. The anisotropy of SSH wavenumber spectral slopes implies that EKE distributes anisotropically in different directions, and this distribution is closely associated with the generation and nonlinear evolution of mesoscale movements.

The coupling of hemin with persistent free radicals induces a nonradical mechanism for oxidation of pollutants.

Herein, we report that persistent free radicals (PFRs) based on MWCNTs significantly accelerate the pollutant removal rate. EPR measurement combined with the electrochemical test indicated that a nonradical mechanism was responsible for the enhancement, which is different from the previously reported radical pathway on PFRs.

Banded structure of drifting macroalgae.

A massive bloom of macroalgae occurred in the western Yellow Sea at the end of May, 2008, and lasted for nearly 2 months. The surface-drifting macroalgae was observed to accumulate in a pattern dominated by linear bands. The maximum length of individual algal bands exceeded 10 km and the distance between neighboring bands ranged from hundreds of meters to 6 km. Seven satellite images were analyzed to determine the distances between neighboring bands. Proportions of about 24%, 38%, and 22% are responsible for the separation distances smaller than 1 km, between 1 and 2 km, and between 2 and 3 km, respectively. The separation of about five percent of the bands exceeds 4 km. The probability distribution of the separation distance is quite close to log-normal which is that found in Langmuir circulation. However, the observed algal band separation greatly exceeds the distances between convergence lines reported in Langmuir circulation.