Latest ArticlesSingle-atom nanozymes (SANs) have attracted extensive attention due to their characteristics of both single-atom catalysts (SACs) and enzymes. Using spin-polarized density functional theory (DFT) calculations combined with the hybrid solvation model, this work designed a series of carbon-supported Group Ⅷ transition metals TMS4-C SANs, similar to the TMS4 active center of formate dehydrogenase (FADH), aiming to develop highly efficient SANs for CO2 electroreduction. DFT calculations show that compared with TMN4-C, TMS4-C have FADH-like feature, which can selectively reduce CO2 to formic acid. Particularly, CoS4-C is the most promising SAN for CO2 reduction, with a low limiting potential of -0.07 V, which exceeds most reported catalysts. Two descriptors of TMX4-C (X = N, S) based on intrinsic and electronic structure properties were proposed to shed light on the origin activity of candidates. The findings presented here will provide new insights into the design of novel enzyme-like catalysts for electrochemical CO2 reduction.
Benefitting from the development of non-fullerene acceptors (NFAs), remarkable advances have been achieved with the power conversion efficiency (PCE) exceeding 19% over the last few years. However, the major achievement comes from fused ring electron acceptors (FREAs) with complex structures, leading to high cost. Hence, it is urgent to design new materials to resolve the cost issues concerning basic commercial requirements of organic solar cells. Recently, great progress has been made in fully non-fused ring electron acceptors (NFREAs) with only single-aromatic ring in the electron-donating core, which might achieve a fine balance between the efficiency and cost, thus accelerating the commercial application of organic solar cells. Therefore, this article summarizes the recent advances of fully NFREAs with efficiency over 10%, which may provide a guidance for developing the cost-effective solar cells.
Rapid detection of foodborne pathogens is crucial to prevent the outbreaks of foodborne diseases. In this work, we proposed a novel microfluidic biosensor based on magnetorheological elastomer (MRE) and smartphone. First, micropump and microvalves were constructed by deforming the MRE under magnetic actuation and integrated into the microfluidic biosensor for fluidic control. Then, the micropump was used to deliver immune porous gold@platinum nanocatalysts (Au@PtNCs), bacterial sample, and immunomagnetic nanoparticles (MNPs) into a micromixer, where they were mixed, incubated and magnetically separated to obtain the Au@PtNC-bacteria-MNP complexes. After 3, 3′, 5, 5′-tetramethylbenzidine and hydrogen peroxide were injected and catalyzed by the Au@PtNCs, smartphone was used to measure the color of the catalysate for quantitative analysis of target bacteria. Under optimal conditions, this biosensor could detect Salmonella typhimurium quantitatively and automatically in 1 h with a linear detection range of 8.0 × 101 CFU/mL to 8.0 × 104 CFU/mL and a detection limit of 62 CFU/mL. The microfluidic biosensor was compact in size, simple to use, and efficient for detection, and might be used for in-field screening of foodborne pathogens to prevent food poisoning.
Materials with facilely tunable spin configurations based on metal-radical coordination systems have potential applications for electronics and spintronics. Here, we report the ground state conversion of copper corrole radicals from singlet to triplet via the extension of the π-conjugation system by benzo-fusion at the β-position of corrole ligand. NMR spectroscopy, SQUID measurements and computational studies all support the ferromagnetic coupling between the Cu(Ⅱ) center and corrole π-radical of benzo-fused copper corrole 2-Cu, which is in sharp contrast with the antiferromagnetic coupling in regular non-extended copper corroles. The triplet 2-Cu is highly stable in air, and X-ray diffraction analysis revealed its unique highly planar corrole macrocycle. This work offers a promising strategy for creating high-spin systems in non-innocent metallocorroles.
The self-assembled behavior of an unsymmetric molecule (BCDTDA) with one imidazole group as center and benzoic acid group as functional group is studied, and the regulatory behaviors of coronene (COR) and three bipyridine derivatives (named BP, PEBP-C4 and PEBP-C8) on BCDTDA self-assembly structures are also investigated. Based on highly oriented pyrolytic graphite (HOPG) substrate, scanning tunneling microscopy (STM) is used to observe the variation of assembled behaviors at the solid-liquid interface. Because of the concentration effect, BCDTDA molecules can assemble into grids and Kagomés structures in the form of NH···O hydrogen bonded dimers. BCDTDA molecules still maintain dimeric structures in the regulation of COR and BP molecules to BCDTDA self-assembly. However, PEBP-C4 and PEBP-C8 destroy the structure of the dimers, and form a variety of co-assembled structures with BCDTDA. Different guest molecules coordinate the host molecules differently, which makes the experiment more meaningful. Combined with density functional theory (DFT) calculation, the discovery of molecular interactions provides a promising strategy for the construction of functional nanostructures and devices.
Circularly polarized light (CPL) is an inherently chiral entity and is regarded as one of the possible deterministic signals that led to the evolution of homochirality in earth. Thus, CPL as an external physical field has been widely used in a technique known as absolute asymmetric synthesis, because a product enriched in one enantiomer is formed from racemic precursor molecules without the intervention of a chiral catalyst. In this review, we retrospect the historical research of CPL-induced absolute asymmetric synthesis, including chiral organic molecules, helical polymers, supramolecular assemblies, noble metal nanostructures. However, based on these results, we concluded that the chiral photon-matter interaction is very faint due to the arrangement of molecular bonds giving rise to chiral features, is over a smaller distance than the helical pitch of CPL, leading extremely small enantiomeric excess for product. Therefore, we highlight the recently emerged technology called superchiral field, in which the superchiral far-field and near-field could enhance the dissymmetry of optical field and near-field, respectively. In sum, we hope this review could bring some enlightenment to researchers and further improve the enantioselectivity of CPL-induced absolute asymmetric synthesis.
Anthropogenic carbon dioxide (CO2) emission from the combustion of fossil fuels aggravates the global greenhouse effect. The implementation of CO2 capture and transformation technologies have recently received great attention for providing a pathway in dealing with global climate change. Among these technologies, electrochemical CO2 capture technology has attracted wide attention because of its environmental friendliness and flexible operating processes. Bipolar membranes (BPMs) are considered as one of the key components in electrochemical devices, especially for electrochemical CO2 reduction and electrodialysis devices. BPMs create an alkaline environment for CO2 capture and a stable pH environment for electrocatalysis on a single electrode. The key to CO2 capture in these devices is to understand the water dissociation mechanism occurring in BPMs, which could be used for optimizing the operating conditions for CO2 capture and transformation. In this paper, the references and technologies of electrochemical CO2 capture based on BPMs are reviewed in detail, thus the challenges and opportunities are also discussed for the development of more efficient, sustainable and practical CO2 capture and transformation based on BPMs.
π-Electron coupling of pendant conjugated segment in π-stacked semiconducting polymers always causes the formation of defect trapped sites and further quenched high-band excitons, which is harmful to the performance and stability of deep-blue polymer light-emitting diodes (PLEDs). Herein, considerate of “defect” carbazole (Cz) electromers in poly(N-vinylcarbazole) (PVK), a series of fluorene units are introduced into pendant segments (PVCz-DMeF, PVCz-FMeNPh and PVCz-DFMeNPh) to suppress the strong π-electron coupling of pendant Cz units and enhance radiative transition toward fabricating sable PLEDs. Compared to PVCz-FMeNPh and PVCz-DFMeNPh, PVCz-DMeF spin-coated films show a relatively efficient deep-blue emission, completely similar to its single pendant chromophore, confirmed an extremely weak charge-transfer and electron coupling between adjacent pendant segments. Therefore, PLEDs based on PVCz-DMeF present stable and deep-blue emission with a high color purity (0.17, 0.08), associated with extremely weak defect emission at 600~700 nm (induced by carbazole electromers). Finally, PLEDs based on PVCz-DMeF/F8BT blended films (1:1) also present the high maximum luminance (Lmax) of 6261 cd/m2 and current efficiency (CEmax) of 2.03 cd/A, confirmed slightly trapped sites formation. Therefore, precisely control the arrangement and packing model of pendant units in π-stacked polymer is an essential prerequisite for building efficient and stable emitter for optoelectronic devices.
To achieve real-time monitoring of humidity in various applications, we prepared facile and ultra-thin CoAl layered double hydroxide (CoAl LDH) nanosheets to engineer quartz crystal microbalances (QCM). The characteristics of CoAl LDH were investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectric spectroscopy (XPS), Brunauer–Emmett–Telle (BET), atomic force microscopy (AFM) and zeta potential. Due to their large specific surface area and abundant hydroxyl groups, CoAl LDH nanosheets exhibit good humidity sensing performance. In a range of 11.3% and 97.6% relative humidity (RH), the sensor behaved an ultrahigh sensitivity (127.8 Hz/%RH), fast response (9.1 s) and recovery time (3.1 s), low hysteresis (3.1%RH), good linearity (R2 = 0.9993), stability and selectivity. Besides, the sensor can recover the initial response frequency after being wetted by deionized water, revealing superior self-recovery ability under high humidity. Based on in-situ Fourier transform infrared spectroscopy (FT-IR), the adsorption mechanism of CoAl LDH toward water molecules was explored. The QCM sensor can distinguish different respiratory states of people and wetting degree of fingers, as well as monitor the humidity in vegetable packaging, suggesting excellent properties and a promising application in humidity sensing.
Owing to their unique design and development, high safety and low-cost efficient cathode is still at the forefront of research for rechargeable zinc-ion batteries. However, the suitable cathode operating with ultrahigh capacity with a dendrite-free anode reaction mechanism remains challenging. In this, the first archetype of a high-rate and morphologically stabled cathode material is constructed from novel cauliflower-like nano-ZnV2S4 for aqueous zinc-ion batteries. Thus, nano-ZnV2S4 was prepared with an anion exchange reaction using ZnV2(OH)8 cauliflower-like nanostructured array as a template interestingly no morphological and shape changes were detected. The as-prepared nano-ZnV2S4 electrode reveals a specific discharge capacity of 348.2 mAh/g during 0.5 A/g with enhanced rate capability and excellent capacity retention of 89.2% at 4 A/g current density even after completing 1000 cycles.