Corannulene derivatives for organic electronics: From molecular engineering to applications

This paper intends to provide an overview for using corannulene derivatives in organic electronics such as organic field-effect transistors (OFETs), organic solar cells (OSCs), and organic light-emitting diodes (OLEDs). We highlight the rational design strategies, tuning molecular orbital energy levels and arrangement in single crystals of corannulenes. The topological structure and properties of corannulene make it a unique candidate for organic electronics.     

Complementarity between micro-micro and micro-macro entanglement in a Bose–Einstein condensate with two Rydberg impurities

We theoretically study complementarity between micro-micro and micro-macro entanglement in a Bose–Einstein condensate with two Rydberg impurities. We investigate quantum dynamics of micro-micro and micro-macro entanglement in the micro-macro system. It is found that strong micro-macro entanglement between Rydberg impurities and the BEC can be generated by the use of initial micro-micro entanglement between two Rydberg impurities, which acts as the seed entanglement to create micro-macro entanglement. We demonstrate a curious complementarity relation between micro-micro and micro-macro entanglement, and find that the complementarity property can be sustained to some extent even though in the presence of the BEC decoherence.     

An Ultrasensitive Electrochemical Immunosensor for Nonylphenol Leachate from Instant Noodle Containers in Southeast Asia

Nonylphenols (NPNs) are persistent endocrine disruptors and their release into the environment is causing increasing concern about their impact on human health. Herein, an ultrasensitive electrochemical immunosensor was developed for the detection of NPNs in the leachates from 61 instant noodle containers (INCs) from 8 countries across Southeast Asia. Gold nanoclusters (AuNCs) were self-assembled with reduced graphene oxide (rGO; polyethylenimine–rGO) and used to modify a glassy carbon electrode (GCE), which showed excellent electrical conductivity. An anti-NPN antibody was then immobilized on the AuNCs and, if it specifically bound NPN, the reduction in conductivity of the GCE was remarkable. The designed immunosensor has a low detection limit (5.25 ng L⁻¹) and high sensitivity for NPNs in the leachates of INCs. Remarkably, the leaching of estrogen-like compounds from different plastics of INCs and the correlation between NPN content and total estrogenic activity were thoroughly investigated. High temperatures caused polyethylene and polystyrene INCs to release more estrogen-like compounds than that of polypropylene INCs; this increased release of NPNs was associated with higher estrogen activity in living cells. These data fill the gap in human and environmental exposure to estrogen-like compounds through INCs.     

MOF Encapsulated AuPt Bimetallic Nanoparticles for Improved Plasmonic-induced Photothermal Catalysis of CO2 Hydrogenation

Exploring new catalytic strategies for achieving efficient CO₂ hydrogenation under mild conditions is of great significance for environmental remediation. Herein, a composite photocatalyst Zr-based MOF encapsulated plasmonic AuPt alloy nanoparticles (AuPt@UiO-66-NH₂) was successfully constructed for the efficient photothermal catalysis of CO₂ hydrogenation. Under light irradiation at 150 °C, AuPt@UiO-66-NH₂ achieved a CO production rate of 1451 μmol g_metal⁻¹ h⁻¹ with 91 % selectivity, which far exceeded those obtained by Au@Pt@UiO-66-NH₂ with Pt shell on Au (599 μmol g_metal⁻¹ h⁻¹) and Au@UiO-66-NH₂ (218 μmol g_metal⁻¹ h⁻¹). The outstanding performances of AuPt@UiO-66-NH₂ were attributed to the synergetic effect originating from the plasmonic metal Au, doped active metal Pt, and encapsulation structure of UiO-66-NH₂ shell. This work provides a new way for photothermal catalysis of CO₂ and a reference for the design of high-performance plasmonic catalysts.     

Iron Nanoparticles Protected by Chainmail-structured Graphene for Durable Electrocatalytic Nitrate Reduction to Nitrogen

The electrochemical nitrate reduction reaction (NO₃RR) is an appealing technology for regulating the nitrogen cycle. Metallic iron is one of the well-known electrocatalysts for NO₃RR, but it suffers from poor durability due to leaching and oxidation of iron during the electrocatalytic process. In this work, a graphene-nanochainmail-protected iron nanoparticle (Fe@Gnc) electrocatalyst is reported. It displays superior nitrate removal efficiency and high nitrogen selectivity. Notably, the catalyst delivers exceptional stability and durability, with the nitrate removal rate and nitrogen selectivity remained ≈96 % of that of the first time after up to 40 cycles (24 h for one cycle). As expected, the conductive graphene nanochainmail provides robust protection for the internal iron active sites, allowing Fe@Gnc to maintain its long-lasting electrochemical nitrate catalytic activity. This research proposes a workable solution for the scientific challenge of poor lasting ability of iron-based electrocatalysts in large-scale industrialization.     

Reactive Polymer as Artificial Solid Electrolyte Interface for Stable Lithium Metal Batteries

Lithium (Li) metal anodes have the highest theoretical capacity and lowest electrochemical potential making them ideal for Li metal batteries (LMBs). However, Li dendrite formation on the anode impedes the proper discharge capacity and practical cycle life of LMBs, particularly in carbonate electrolytes. Herein, we developed a reactive alternative polymer named P(St-MaI) containing carboxylic acid and cyclic ether moieties which would in situ form artificial polymeric solid electrolyte interface (SEI) with Li. This SEI can accommodate volume changes and maintain good interfacial contact. The presence of carboxylic acid and cyclic ether pendant groups greatly contribute to the induction of uniform Li ion deposition. In addition, the presence of benzyl rings makes the polymer have a certain mechanical strength and plays a key role in inhibiting the growth of Li dendrites. As a result, the symmetric Li||Li cell with P(St-MaI)@Li layer can stably cycle for over 900 h under 1 mA cm⁻² without polarization voltage increasing, while their Li||LiFePO₄ full batteries maintain high capacity retention of 96 % after 930 cycles at 1C in carbonate electrolytes. The innovative strategy of artificial SEI is broadly applicable in designing new materials to inhibit Li dendrite growth on Li metal anodes.     

Mechanism of Cations Suppressing Proton Diffusion Kinetics for Electrocatalysis

Proton transfer is crucial for electrocatalysis. Accumulating cations at electrochemical interfaces can alter the proton transfer rate and then tune electrocatalytic performance. However, the mechanism for regulating proton transfer remains ambiguous. Here, we quantify the cation effect on proton diffusion in solution by hydrogen evolution on microelectrodes, revealing the rate can be suppressed by more than 10 times. Different from the prevalent opinions that proton transport is slowed down by modified electric field, we found water structure imposes a more evident effect on kinetics. FTIR test and path integral molecular dynamics simulation indicate that proton prefers to wander within the hydration shell of cations rather than to hop rapidly along water wires. Low connectivity of water networks disrupted by cations corrupts the fast-moving path in bulk water. This study highlights the promising way for regulating proton kinetics via a modified water structure.     

基于石墨烯的毒死蜱分子印迹电化学传感器的制备及对毒死蜱的测定

利用分子印迹技术,以马来松香丙烯酸乙二醇酯为交联剂,使用自由基热聚合法在石墨烯修饰的玻碳电极表面合成毒死蜱( CPF)分子印迹聚合膜,制得了CPF分子印迹电化学传感器。采用循环伏安法、线性扫描伏安法和电化学交流阻抗法等,考察了此CPF分子印迹膜的电化学性能。在最佳检测条件下,传感器的峰电流与CPF浓度在2.0×10-7~1.0×10-5mol/L范围内呈线性关系,线性方程为Ip(μA)=-7.1834-0.2424C (μmol/L),相关系数r2=0.9959,检出限为6.7×10-8 mol/L(S/N=3)。构建了CPF分子印迹电化学传感器的动力学吸附模型,测得印迹传感器的印迹因子β=2.59,结合速率常数k=12.2324 s。传感器表现出良好的重现性和稳定性,并成功用于实际水样和蔬菜样品中CPF的测定,加标回收率为94.1%~101.4%。