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  • Yue Zhao, Zhi Gu, Wei Weng, Dan Zhou, Ziqiang Liu, Wentong Fan, Shungui Deng, Hao He, Xiayin Yao
    Chinese Chemical Letters. 2023, 34(2): 107232-.

    The polysulfide shuttle limits the development of lithium-sulfur (Li-S) batteries with high energy density and long lifespan. Herein, nitrogen doped hollow carbon nanospheres (NHCS) derived from polymerization of dopamine on SiO2 nanospheres are employed to modify the commercial polypropylene/polyethylene/polypropylene tri-layer separators (PP/PE/PP@NHCS). The abundant nitrogen heteroatoms in NHCS exhibit strong chemical adsorption toward polysulfides, which can effectively suppress the lithium polysulfides shuttle and further enhance the utilization of active sulfur. Lithium-sulfur batteries employing the PP/PE/PP@NHCS deliver an initial discharge capacity of 1355 mAh/g and retain high capacity of 921 mAh/g after 100 cycles at 0.2 C. At a high rate of 2 C, the lithium-sulfur batteries exhibit capacity of 461 mAh/g after 1000 cycles with a capacity fading rate of 0.049% per cycle. This work demonstrates that the NHCS coated PP/PE/PP separator is promising for future commercial applications of lithium-sulfur batteries with improved electrochemical performances.

  • Di Huang, Daxiong Wu, Jixing Zhu, Jinyu Xie, Jipeng Wu, Jiaojiao Liang
    Chinese Chemical Letters. 2023, 34(2): 107416-.

    One-dimensional carbon nanofibers are widely applied as anode material in the energy storage field due to its unique structure and high conductivity. In this work, one-dimensional ZnSe@N-doped carbon nanofibers (ZnSe@NC NFs) are successfully synthesized by electrospinning and annealed without extra troublesome conditions. ZnSe nanocrystals are enfolded in the N-doped carbon nanofibers, which can act as a protective layer to avoid the volume expansion of active material and promote ion transport during the cycling process. More importantly, the as-synthesized ZnSe@NC NFs are served as the anode material and display the admirable storage properties for Na/K-ion batteries. The one-dimensional ZnSe@NC NFs material shows the high capacity of 237 mAh/g for Na-ion batteries at a current density of 1 A/g for 2000 cycles. Meanwhile, it also delivers a high discharge capacity of 337 mAh/g for K-ion batteries at 0.2 A/g for 300 cycles. Additionally, it is confirmed that the pseudocapacitive contribution of the nano-structure material is up to 54.5% at a scan rate of 0.6 mV/s through the cyclic voltammetry (CV) measurement in K-ion batteries.

  • Jinxing Ma, Jiazhou He, Xiangtong Kong, Junjian Zheng, Lanfang Han, Yi Liu, Zhenchang Zhu, Zhong Zhang
    Chinese Chemical Letters. 2023, 34(2): 107407-.

    The growing food delivery service market has boosted the consumption of packaging materials, and this trend is projected to continue in the following years. The gap between industrial supply and consumer demand from a sustainable viewpoint leads to a need for agricultural cellulosic waste-based materials that bring the idea of trash-to-treasure to fruition. In this paper, we review up-to-date advancements surrounding the food delivery packaging that are derived from agricultural cellulosic waste. Two scenarios in which agricultural feedstock is used as a host or guest material are summarized, and sketch on the individual processing routine is depicted. We further evaluate how the chemical compositions and processing parameters influence the properties of the final products. Current challenges and gaps in developing sustainable packaging materials are identified, with perspectives on these important issues highlighting the importance of process innovation as well as economic and environmental-impact assessment for agricultural cellulosic waste to food delivery packaging.

  • Zihao Li, Xianggui Zhou, Subhash Singh, Xiaoming Wei, Chunlei Guo, Weishan Li
    Chinese Chemical Letters. 2023, 34(2): 107230-.

    Platinum exhibits high electrocatalytic activity toward various reactions but might be poisoned by some species. This communication reports a new finding that the electrocatalytic activity of platinum for methanol oxidation will be largely lost in a lead-contaminated environment. This activity loss is demonstrated in an electrochemical cell using a lead counter electrode for measuring the activity of platinum electrode towards methanol oxidation. The recorded methanol oxidation current in this cell is significantly decreased compared with that using a platinum counter electrode. The possible mechanism is related to the adsorption of trace lead ions from the lead counter electrode, as confirmed by comparing the calculated binding energies of platinum and lead ions with oxygen ion. This report is of great importance for reliably designing and efficiently managing direct methanol fuel cells, because trace lead might be present in various components in the fuel cell systems or in air and attention should be paid to its negative effect.

  • Zepeng Zhang, Yunyun Li, Longzhang Dong, Zhonglong Yin, Ziqi Tian, Weiben Yang, Zhen Yang
    Chinese Chemical Letters. 2023, 34(2): 107404-.

    Hydroxyl radicals (OH) generated on anode play a vital role in electrochemical oxidation (EO) of organic pollutants for water treatment. Inspired by the four-electron oxygen evolution reaction (OER), we supposed an anode-selection strategy to stabilize deeply oxidized states (*O and *OOH) which are beneficial to generating OH. To verify the hypothesis, a candidate anode component (MIL-101(Cr), a well-known metal-organic framework with active variable-valence transition metal centers) was used to coat Ti/TiO2 plate to fabricate anodes. Compared to TiO2(101) plane on undecorated anode surface, fast and complete removal of aniline and phenol, and improved energy utilization were achieved on MIL-101(Cr)-coated-Ti/TiO2 anode. Mechanism investigation, including pollutant degradation pathways, showed the predominate contribution (69.60%–75.13%) of OH in pollutant mineralization. Density functional theory (DFT) computations indicated Cr site in MIL-101(Cr) was more conducive to stabilizing *O and *OOH, leading to thermodynamical spontaneous generation of OH. This work opens up an exciting avenue to explore OH production, and supplies a useful guidance to the development of anode materials for EO process.

  • Yong Zhao, Wei Cheng, Jiahan Wu, Zhengguang Hu, Fengliang Liu, Li Wang, Honggen Peng
    Chinese Chemical Letters. 2023, 34(2): 107413-.

    Lithium-oxygen (Li-O2) batteries are considered as the next generation for energy storages systems due to the higher theoretical energy density than that of Li-ion batteries. However, the high charge overpotential caused by the insulated Li2O2 results in low energy efficiency, side reaction from electrolyte and cathode, and therefore poor battery performance. Designing noble metal-based catalysts can be an effective strategy to develop high-performance Li-O2 batteries with low charge overpotentials and outstanding cycle stability. However, the charge mechanism for noble metal-based catalysts is not clear and even contradictory. Herein, several charge mechanisms of Li2O2 are first discussed. Subsequently, the possible charge processes of Li-O2 batteries with noble metal-based catalysts are illustrated. In addition, the future development for noble metal-based catalysts is outlined.

  • Jiying Huang, Yujian Yan, Yuyi Ou, Yanyan Jia, Lianpeng Sun, Qing Zhao, Hui Lu
    Chinese Chemical Letters. 2023, 34(2): 107433-.

    The removal of eight typical pharmaceuticals (PhACs) (i.e., ibuprofen (IBU), ketoprofen (KET), diclofenac (DIC), sulfadiazine (SD), sulfamethoxazole (SMX), trimethoprim (TMP), ciprofloxacin (CIP) and enoxacin (ENO)) in sulfur-driven autotrophic denitrification (SdAD) process were firstly investigated via long-term operation of bioreactor coupled with batch tests. The results indicated that IBU and KET can be effectively removed (removal efficiency > 50%) compared to other six PhACs in SdAD bioreactor. Biodegradation was the primary removal route for IBU and KET with the specific biodegradation rates of 5.3±0.7~18.1±1.8 µg g−1-VSS d−1 at initial concentrations of 25-200 µg/L. The biotransformation intermediates of IBU and KET were examined, and the results indicated that IBU was biotransformed to three intermediates via hydroxylation and carboxylation. KET biotransformation could be initiated from the reduction of the keto group following with a series of oxidation/reduction reactions, and five intermediates of KET were observed in this study. The microbial community composition in the system was markedly shifted when long-term exposure to PhACs. However, the functional microbes (e.g., genus Thiobacillus) showed high tolerance to PhACs, resulting in the high efficiency for PhACs, N and S removal during long-term SdAD reactor operation. The findings provide better insight into PhACs removal in SdAD process, especially IBU and KET, and open up an innovative opportunity for the treatment of PhACs-laden wastewater using sulfur-mediated biological process.

  • Cunli Wang, Xue Wang, Dongdong Wang, Shengxu Qian, Fusheng Zhang, Mingyang Li, Minmin Li, Wenqi Lu, Bo Liu, Guangyan Qing
    Chinese Chemical Letters. 2023, 34(2): 107332-.

    Prion diseases are fatal neurodegenerative diseases that can cause severe dementia. The misfolding and accumulation of the prion peptide (PrP)106–126 is crucial, and this process is closely relevant to biological membranes. However, how PrP106–126 aggregation is affected by the molecular chirality of phospholipid membrane is unknown. Thus, in this study, a pair of L- and D-aspartic acid (Asp)-modified 1, 2-dipalmitoyl-sn-glycero-3-phosphoethanolamine (DPPE) were synthesized to construct chiral liposomes. We discover that L-Asp-DPPE liposomes strongly inhibit the oligomerization and amyloidogenesis of PrP106–126, whether acting on monomers or oligomers, which rescues cytotoxicity induced by PrP106–126. By comparison, D-Asp-DPPE liposomes inhibit peptide oligomerization only at a high concentration and cannot prevent amyloidogenesis when acting on oligomers, which lead to pronounced cytotoxicity. Apoptosis experiment, dynamic change of intracellular Ca2+ (iCa2+) and Ca2+ release from endoplasmic reticulum (ER), reactive oxygen species (ROS) production, adsorption dynamics and affinity tests, and fluorescent imaging clearly disclose that molecular chirality of the liposomes dominates conformational transition of PrP106–126 from random coil to β-sheet, binding and adsorption of the monomers and oligomers, and subsequent fibrillation process, resulting in distinct inhibition effect in Ca2+ overload and release, ROS production and cell apoptosis. This work is the first to report that interfacial molecular chirality is a potentially crucial influence on the fibrillation process of PrP106–126 and its cell responses, whereas the convergence of chiral amino acids and liposomes can be considered potential inhibitors in prion diseases.

  • Jiayuan Zhang, Xinyu Wang, Gui Wang, Yi Feng, Chunhui Zhang, Tao Pang, Guanggang Gao, Linlin Fan, Hong Liu
    Chinese Chemical Letters. 2023, 34(2): 107231-.

    Polyoxometalates (POMs) are important inorganic photochromic materials to be potentially applied in photo-induced switch, energy storage, and even the detection of light. However, due to the limited sensitivity of POMs, it is difficult to realize the photochromic response to weak visible light. In this paper, by the coordination of solvated Pb(II), a new structure-defined chain-like polyoxomolybdate complex of [(Pb(DMF)4)3(P2Mo18O62)2]n (Pb3Mo18, DMF = dimethylformamide) has been demonstrated by a facile solvent-diffusion approach. By virtue of interactions between Pb(DMF)4 and polyoxoanions, Pb3Mo18 shows an ultrasensitive photochromic response to weak visible lights and forms the reduced 'heteropoly blue' species through ligand-to-metal charge transfer (LMCT) process. A new mechanism is firstly proposed here that the 6s orbital lone electron pair on Pb(II) can effectively stabilize the generated hole of oxygen atoms as a result of O→Mo charge transfer. Through the proposed mechanism, the LMCT barrier is drastically lowered and allows the coloration to be occurred even upon weak visible light. Also, because the conductivity of Pb3Mo18 enhances with the increase of reduction extent, its electrochemical impedance signals are proportionally response to irradiation intensity. Especially, for the first time, the polyoxomolybdate composite can be used to detect weak visible light, in which the optical signal can be converted into electrical signal output. Moreover, Pb3Mo18 can be drip-coated on the surface of the screen printed chip electrode, which is facile to the detection of light by portable devices compatible with computers, mobile phones and other electronic equipment. This work not only highlights a new approach to the molecular design of photochromic POMs by the coordination of metal ions with the effect of inert electron pair, but also lays a foundation to extend the application of POMs as light signal sensors.

  • Zhipeng Xu, Yao Ni, Hong Han, Huanhuan Wei, Lu Liu, Shuo Zhang, Hao Huang, Wentao Xu
    Chinese Chemical Letters. 2023, 34(2): 107292-.

    Artificial synapses with full synapse-like functionalities are of crucial importance for the implementation of neuromorphic computing and bioinspired intelligent systems. In particular, the development of artificial synapses with the capability to emulate multiplexed neural transmission is highly desirable, but remains challenging. In this work, we proposed a hybrid ambipolar synaptic transistor that combines two-dimensional (2D) molybdenum disulfide (MoS2) sheet and crystalline one-dimensional (1D) poly(3-hexylthiophene-2, 5-diyl) polymer nanowires (P3HT NWs) as dual excitatory channels. Essential synaptic functions, including excitatory postsynaptic current, paired-pulse facilitation, synaptic potentiation and depression, and dynamic filtering were emulated using the synaptic transistor. Benefitting from the dual excitatory channels of the synaptic transistor, the device achieved a fast switch between short-term and long-term memory by altering the charge carriers in the dual channels, i.e., electrons and holes. This emulated the multiplexed neural transmission of different excitatory neurotransmitters, e.g., dopamine and noradrenaline. The plasticity-switchable artificial synapse (PSAS) simulates the task-learning process of individuals under different motivations and the impact of success or failure on task learning and memory, which promises the potential to enable complex functionalities in future neuromorphic intelligent electronics.

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