Hydrogen-Bond-Enhanced Photoreforming of Biomass Furans over a Urea-Incorporated Cu(II) Porphyrin Framework.

Solar-driven upgrading of biomass-derived 5-hydroxylmethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) holds great promise for sustainable production of bio-plastics and resins. However, the process is limited by poor selectivity and sluggish kinetics due to the vertical coordination of HMF at relatively strong metal sites. Here, we purposely developed a Cu(II) porphyrin framework featuring side-chain incorporated urea linkages, denoted as TBUPP-Cu MOF, to render HMF a weak hydrogen bond at the urea site and flat adsorption via π-π stacking with the benzene moiety. The unique configuration promotes the approaching of -CHO of HMF to the photoexcited porphyrin ring towards kinetically and thermodynamically favourable intermediate formation and subsequent desorption. The charge localisation and orbital energy alignment enable the selective activation of O2 over the porphyrin to generate ⋅O2 - and 1O2 instead of highly oxidative H2O2 and ⋅OH via spin-flip electron transfer, which drive the ambient oxidation of proximal -CHO. The effective utilisation of redox species and circumvented over-oxidation facilitate a FDCA selectivity of >90 % with a high turnover number of 193 molHMF molCu -1. The facile purification of high-purity FDCA and zero-waste recycling of intermediates and durable catalyst feature TBUPP-Cu MOF a promising photo-oxidation platform towards net-zero biorefining and organic transformations.

Linkage Engineering in Covalent Organic Frameworks for Metal-Free Electrocatalytic C2H4 Production from CO2.

Electrocatalytic carbon dioxide reduction reaction (CO2RR) to produce ethylene (C2H4) is conducive to sustainable development of energy and environment. At present, most electrocatalysts for C2H4 production are limited to the heavy metal copper, meanwhile, achieving metal-free catalysis remains a challenge. Noted piperazine with sp3 N hybridization is beneficial to CO2 capture, but CO2RR performance and mechanism have been lacking. Herein, based on linkage engineering, we construct a novel high-density sp3 N catalytic array via introducing piperazine into the crystalline and microporous aminal-linked covalent organic frameworks (COFs). Thanks to its high sp3 N density, strong CO2 capture capacity and great hydrophilicity, aminal-linked COF successfully achieves the conversion of CO2 to C2H4 with a Faraday efficiency up to 19.1 %, which is stand out in all reported metal-free COF electrocatalysts. In addition, a series of imine-linked COFs are synthesized and combined with DFT calculations to demonstrate the critical role of sp3 N in enhancing the kinetics of CO2RR. Therefore, this work reveals the extraordinary potential of linkage engineering in COFs to break through some catalytic bottlenecks.

Spontaneous self-intercalation of copper atoms into transition metal dichalcogenides.

Intercalated transition metal dichalcogenides (TMDs) have attracted substantial interest due to their exciting electronic properties. Here, we report a unique approach where copper (Cu) atoms from bulk Cu solid intercalate spontaneously into van der Waals (vdW) gaps of group IV and V layered TMDs at room temperature and atmospheric pressure. This distinctive phenomenon is used to develop a strategy to synthesize Cu species-intercalated layered TMD compounds. A series of Cu-intercalated 2H-NbS2 compounds were obtained with homogeneous distribution of Cu intercalates in the form of monovalent Cu (I), occupying the tetrahedral sites coordinated by S atoms within the interlayer space of NbS2. The Fermi level of NbS2 shifts up because of the intercalation of Cu, resulting in the improvement of electrical conductivity in the z-direction. On the other hand, intercalation of Cu into vdW gaps of NbS2 systematically suppresses the superconducting transition temperature (T c) and superconducting volume fraction.

Facile and reversible digestion and regeneration of zirconium-based metal-organic frameworks.

The digestion/regeneration of metal-organic frameworks (MOFs) has important applications for catalysis, drug delivery, environmental decontamination, and energy storage, among other applications. However, research in this direction is limited and very challenging. Here, we develop a facile method to digest and regenerate a series of zirconium-based metal-organic frameworks (Zr-MOFs) by bicarbonate or carbonate salts. As an example, UiO-66 demonstrates well the mechanism of reversible digestion/regeneration processes. By analyzing the digested zirconium species via X-ray diffraction, Fourier transform infrared spectroscopy and Raman scattering spectroscopy, a digestion mechanism based on the formation of dissoluble complexes [Zr2(OH)2(CO3)4]2- is proposed. Impressively, ultrafine Pd nanoparticles can be extracted from Pd@PCN-224 via this strategy. This work, thus, may provide new insight for the development of renewable MOFs and their practical applications.

Three-Dimensional Hierarchical Constructs of MOF-on-Reduced Graphene Oxide for Lithium-Sulfur Batteries.

A three-dimensional (3D) hierarchical MOF-on-reduced graphene oxide (MOF-on-rGO) compartment was successfully synthesized through an in situ reduced and combined process. The unique properties of the MOF-on-rGO compartment combining the polarity and porous features of MOFs with the high conductivity of rGO make it an ideal candidate as a sulfur host in lithium-sulfur (Li-S) batteries. A high initial discharge capacity of 1250 mAh g-1 at a current density of 0.1 C (1.0 C=1675 mAh g-1 ) was reached using the MOF-on-rGO based electrode. At the rate of 1.0 C, a high specific capacity of 601 mAh g-1 was still maintained after 400 discharge-charge cycles, which could be ascribed to the synergistic effect between MOFs and rGO. Both the hierarchical structures of rGO and the polar pore environment of MOF retard the diffusion and migration of soluble polysulfide, contributing to a stable cycling performance. Moreover, the spongy-layered rGO can buffer the volume expansion and contraction changes, thus supplying stable structures for Li-S batteries.

Metal-Organic Frameworks for High Charge-Discharge Rates in Lithium-Sulfur Batteries.

We report a new method to promote the conductivities of metal-organic frameworks (MOFs) by 5 to 7 magnitudes, thus their potential in electrochemical applications can be fully revealed. This method combines the polarity and porosity advantages of MOFs with the conductive feature of conductive polymers, in this case, polypyrrole (ppy), to construct ppy-MOF compartments for the confinement of sulfur in Li-S batteries. The performances of these ppy-S-in-MOF electrodes exceed those of their MOF and ppy counterparts, especially at high charge-discharge rates. For the first time, the critical role of ion diffusion to the high rate performance was elucidated by comparing ppy-MOF compartments with different pore geometries. The ppy-S-in-PCN-224 electrode with cross-linked pores and tunnels stood out, with a high capacity of 670 and 440 mAh g-1 at 10.0 C after 200 and 1000 cycles, respectively, representing a new benchmark for long-cycle performance at high rate in Li-S batteries.

Investigation of RNA interference suppression of matrix metalloproteinase-9 in mouse model of atherosclerosis.

OBJECTIVE: To investigate the effect of RNA interference of matrix metalloproteinase (MMP)-9 on atherosclerosis on atherosclerosis in apolipoprotein E (ApoE)-/- mouse. METHODS: ApoE-/- mouse strain and three cell lines (293T, NIH3T3 and Raw264.7) were used in the present study to investigate the effect of MMP-9 silencing by RNA interference. Thirty 10-week-old ApoE-/- mice were randomly assigned to a control group, lentiviruses with naked vector group and Lentiviruses-MMP-9 intervention group (n = 10). Aortic atherosclerotic plaques of the mice were stained with immunohistochemical techniques, the MMP-9 and high-sensitivity C-reactive protein levels of three groups were detected simultaneously. Expression of MMP-9 was significantly down-regulated in interference group. MMP-9 and high-sensitivity C-reactive protein levels in MMP-9 interference group were significantly lower than that of the control group. CONCLUSION: The expression of MMP-9 is closely related to vulnerability of atherosclerotic plaques. Silencing of MMP-9 expression acts as a positive role in maintenance of atherosclerotic plaque stability. The present study provides novel experimental insight for the treatment of vulnerable plaques in atherosclerosis.

Tailoring nanostructures in micrometer size germanium particles to improve their performance as an anode for lithium ion batteries.

A facile and scalable single-step approach is employed to synthesize a bulk germanium electrode, which consists of nanoscale Ge-grains in ∼5 µm porous powders. This three-dimensional Ge electrode exhibits superior specific capacity (∼1500 mA h g(-1)) and cyclic performance, attributed to its unique lithiation/delithiation processes.

Crystal habit-tuned nanoplate material of Li[Li1/3-2x/3NixMn2/3-x/3]O2 for high-rate performance lithium-ion batteries.

A cathode for high-rate performance lithium-ion batteries (LIBs) has been developed from a crystal habit-tuned nanoplate Li(Li(0.17)Ni(0.25)Mn(0.58))O2 material, in which the proportion of (010) nanoplates (see figure) has been significantly increased. The results demonstrate that the fraction of the surface that is electrochemically active for Li(+) transportation is a key criterion for evaluating the different nanostructures of potential LIB materials.

A lossless compression method for medical image sequences using JPEG-LS and interframe coding.

Hospitals and medical centers produce an enormous amount of digital medical images every day, especially in the form of image sequences, which requires considerable storage space. One solution could be the application of lossless compression. Among available methods, JPEG-LS has excellent coding performance. However, it only compresses a single picture with intracoding and does not utilize the interframe correlation among pictures. Therefore, this paper proposes a method that combines the JPEG-LS and an interframe coding with motion vectors to enhance the compression performance of using JPEG-LS alone. Since the interframe correlation between two adjacent images in a medical image sequence is usually not as high as that in a general video image sequence, the interframe coding is activated only when the interframe correlation is high enough. With six capsule endoscope image sequences under test, the proposed method achieves average compression gains of 13.3% and 26.3% over the methods of using JPEG-LS and JPEG2000 alone, respectively. Similarly, for an MRI image sequence, coding gains of 77.5% and 86.5% are correspondingly obtained.