Latest ArticlesAvailable online two new Ni8Mo8 bimetallic coordination clusters, [Ni4(TC4A)]2[(Mo5ⅤMo3ⅥO24)(PO4)] (+Solvent) (Ni8PMo8, H4TC4A= p-tert-butylthiacalix[4]arene) and [Ni4(TC4A)]2[(Mo5ⅤMo3ⅥO24)(OH)(CO3)] (+Solvent) (Ni8Mo8), were synthesized by solvothermal method and structurally characterized by single-crystal X-ray diffraction, powder X-ray diffraction, FT-IR spectroscopy, and TGA experiments, respectively. The usage of H3PMo12O40 as source for Ni8PMo8 resulted a sandwich like structure built from two Ni4-thiacalix[4]arene units and a Mo8 polyoxometalate with inner spaces of PO43−. Ni8Mo8 with the similar structure to that of Ni8PMo8 is from H2MoO4 starting reagent with OH− and CO32− anions encapsulated in the center. The two clusters can be directly loaded on carbon paper and utilized as working electrodes which showed distinguishable performances for glucose detection and oxidation. This work provides a better understanding of the structure–property relationships in using substituted polyoxometalates for electrochemical applications and is helpful for building calixarene-based or polyoxometalate-based functional materials.
Synthetic conditions and ligands are the key structural defining factors of metal–organic frameworks (MOFs). Therefore, reasonable optimization of these aspects is considered to be an effective means for designing materials with novel structures and target functions. Herein, two novel Co(Ⅱ)-based MOFs, namely [Co(HL)(dibp)]n (HL-8) and {[Co2(L)(OH)(dibp)]·DMA}n (HL-9) (H3L = 2′, 6′-dimethyl-[1,1′-biphenyl]-3,4′,5-tricarboxylic acid; dibp = 4,4′-di(1H-imidazol-1-yl)-1,1′-biphenyl]), have been hydrothermally synthesized and structurally characterized. HL-8 crystallizes in the orthorhombic system (Pna21) with a grid layer structure, while HL-9 crystallizes in the monoclinic P21/n space group assembled through Co4(OH)2 clusters with organic ligands. Remarkably, benefiting from the finite cage-like structure, HL-9 exhibited enhanced performance in carbon dioxide (CO2) adsorption/catalytic transformation and excellent size selectivity during dye molecular adsorption process.
Gel polymer electrolytes (GPEs) are promising alternatives to liquid electrolytes applied in high-energy-density batteries. Here superior SiO2 nanofiber composite gel polymer electrolytes (SNCGPEs) are developed via in-situ ionic ring-opening polymerization of 1,3-dioxolane (DOL) monomers in SiO2 nanofiber membrane (PDOL-SiO2) for lithium metal batteries. The oxygen atoms of PDOL together with Si-O of SiO2 construct a more efficient channel for Li+ migration. Consequently, the lithium ion transference number (tLi+) and ionic conductivity (σ) at 30 ℃ of PDOL-SiO2 are 0.80 and 1.68 × 10−4 S/cm separately. PDOL-SiO2 manifests the electrochemical decomposition potentials of 4.90 V. At 0.5 mA/cm2, Li|PDOL-SiO2|Li cell shows a steady cycling performance for nearly 1400 h. LFP|PDOL-SiO2|Li battery can steadily cycle at 0.5 C with a capacity retention rate of 89% after 200 cycles. While cycling at 2 C, the capacity retention rate can maintain at 78% after 300 cycles. This contribution provides a innovative strategy for accelerating Li+ transportation via designing PDOL molecular chains throughout the SiO2 nanofiber framework, which is crucial for high-energy-density LMBs.
MoS2 is a typical electrocatalyst for hydrogen evolution reaction (HER), but the HER activity is spoilt by intensive adsorption towards H*, which requires further improvement. For n-type MoS2, the construction of p-n heterojunction with p-type MoO3 can reverse this situation, because inner electronic field in p-n heterojunction can facilitate H* desorption. Based on this hypothesis, p-n heterojunction is built between MoS2 and MoO3 with polyoxometalate compound as precursor. The obtained MoO3/MoS2 exhibits excellent HER activity, which only requires 68 mV to obtain 10 mA/cm2. With MoO3/MoS2 as cathode material and Zn slice as anode, Zn-H+ battery is assembled. Its open circuit voltage achieves 1.11 V with short circuit current 151.4 mA/cm2. The peak power density of this Zn-H+ battery reaches 47.6 mW/cm2. When discharge at 10 mA/cm2, the specific capacity and energy density reach 728 mAh/g and 759 Wh/kg. In this process, H2 production rate of Zn-H+ battery achieves 364 μmol/h with Faradic efficiency 97.8%. It realizes H2 production and electricity generation simultaneously.
As a burgeoning research field, ultrasound-responsive materials have attracted intense interest in healthcare research. However, the basic mechanism of sonochemical effect in the quasi-solid state is far from being well understood than those in the solution. Herein, we showcase mechanochemical transformations of europium(Ⅲ) complexes in a supramolecular hydrogel matrix. With the combination of labile terpyridine-europium complexes (TPY-Eu3+) as mechanochromic moieties and an ultrasound-responsive fluorogen (URF) as a molecular tweezer, the hydrogel produces a notable fluorescence change in response to ultrasound. The mechanochemical transformation was elucidated by molecular dynamics (MD) simulations, and fully probed and evidenced by electrochemical experiments, X-ray photoelectron spectroscopy (XPS), and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy.
In the field of organic phototransistor, achieving both broad-spectral and high photosensitivity has always been a big challenge. The innovation of device structure has previously proven to be a possible solution to this problem. Here in this study, a novel organic phototransistor based on a high mobility n-type small molecule as the conducting layer and an isolated bulk heterojunction light-absorbing layer as the floating gate has been demonstrated in this study. With the special designed device structure, the phototransistor shows extremely high sensitivity to broad spectral and weak light irradiation, and the photoresponsivity and photocurrent/dark-current ratio of the device can reach up to 4840 mA/W and 1.8 × 105 respectively. For conclusion, this study suggests a potential way to obtain high-performance phototransistors at room temperature, which will further promote the commercial application of organic phototransistors.
Surface charge transfer doping of graphene plays an important role in graphene-based electronics due to its simplicity, high doping efficiency, and easy-controllability. Here, we demonstrate the effective surface charge transfer hole doping of graphene by using a strong p-type molecular dopant hexacyano-trimethylene-cyclopropane (CN6-CP). The CN6-CP exhibits a very high intrinsic work function of 6.37 eV, which facilitates remarkable electron transfer from graphene to CN6-CP as revealed by in situ photoelectron spectroscopy investigations. Consequently, hole accumulation appears in the graphene layer at the direct contact with CN6-CP. As evidenced by Hall effect measurements, the areal hole density of graphene significantly increased from 8.3 × 1012 cm−2 to 2.21 × 1013 cm−2 upon 6 nm CN6-CP evaporation. The CN6-CP acceptor with strong p-doping effect has great implications for both graphene-based and organic electronics.
The Z-scheme heterostructure for photocatalyst can effectively prolong the lifetime of photogenerated carriers and retain a higher conduction/valence band position, promoting the synergistic coupling of photocatalysis and peroxymonosulfate (PMS) activation. In order to fully utilize the luminous energy and realize the efficient activation of PMS, this work achieved successful construction of NiCo2O4/BiOCl/Bi24O31Br10 ternary Z-scheme heterojunction by simultaneously synthesizing BiOCl and NiCo2O4 with NiCl2 and CoCl2 as the precursors. The intercalated BiOCl could serve as a carrier migration ladder to further achieve the spatial separation of electron-hole pairs, so that the oxidation and reduction processes separately occurred in different regions. Compared with the reported catalysts, the as-prepared composites exhibited the enhanced removal efficiency for tetracycline hydrochloride (TCH) in the visible light/PMS system, with a degradation efficiency of 85.30% in 2 min, and possessed good stability. Z-scheme heterojunction was shown to be beneficial for maximizing the superiority of photo-assisted Fenton-like reaction system. The experimental and characterization results confirmed that both non-radicals (1O2) and radicals (SO5•− and SO4•−) were involved in the reaction process and the SO5•− generated by the oxidation of PMS played a crucial role in the TCH degradation. The possible reaction mechanism was finally proposed. This study provided new insight into the Z-scheme heterostructure to promote the photo-assisted Fenton-like reaction.
Hydrophilic interaction liquid chromatography (HILIC) has been recognized as an effective strategy for glycopeptide enrichment. Hydrophilic materials pave the way to solve the limit of low enrichment capacity and poor selectivity. The present study is the first attempt to combine chitosan (CS) and L-cysteine (L-Cys) to design a novel hydrophilic material focusing on glycopeptide enrichment. CS containing a large number of hydrophilic amino and hydroxyl groups has unique chemical properties, which makes it a very attractive biomaterial for glycopeptide enrichment. The excellent hydrophilicity of zwitterionic molecule L-Cys inspires the idea of anchoring L-Cys onto CS to design a novel hydrophilic material (named as Fe3O4@CS@Au-L-Cys) for the capture of low abundance glycopeptides. To be specific, Au nanoparticles (Au NPs) was introduced into CS-coated Fe3O4 via electrostatic interaction and served as bridges to anchor L-Cys onto the surface of CS through strong Au-S bond interaction. The prepared Fe3O4@CS@Au-L-Cys exhibited strong affinity, low detection limit (0.5 fmol/µL HRP), high selectivity (HRP/BSA with a molar ratio of 1:1000) for glycopeptides. Moreover, successful application of glycopeptide enrichment in human serum and saliva by Fe3O4@CS@Au-L-Cys was achieved. A satisfactory data set indicates that Fe3O4@CS@Au-L-Cys has promising potential in the application of glycopeptide enrichment in real complex bio-samples and for related glycoproteome research.
Ammonia is the feedstock chemical for most fertilizers and the alternative of renewable energy carriers. Environmentally benign electrochemical nitrogen reduction reaction (NRR) under mild conditions has been recognized as one of the most attractive strategies for N2 fixation. Herein, inspired by Mo-based nitrogenase, W/Mo-doping electrocatalysts were developed with mixed-metal polyoxometalate H3PW6Mo6O40 as the precursor for high performance electrocatalytic NRR. Trace amount of Pt was transplanted on the surface of W/Mo@rGO via in situ electroplating treatment to further improve the NRR performance. The resulting Pt-W/Mo@rGO-6 achieves excellent performance for NRR with a high NH3 yield of 79.2 µg h−1 mgcat−1 due to the multicomponent synergistic effect in the composite catalyst. The Pt-W/Mo@rGO-6 represents the first example of highly efficient NRR electraocatalyst derived from mixed-metal polyoxometalate, which exhibits outstanding stability confirmed by the constant catalytic performance over 24 h chronoamperometric test. This finding opens a new avenue to construct highly efficient NRR electrocatalyst by employing mixed metal polyoxometalate as the precursor under ambient conditions.
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