A self‐adaptive intelligence gray prediction model with the optimal fractional order accumulating operator and its application

The self‐adaptive intelligence gray predictive model (SAIGM) has an alterable‐flexible model structure, and it can build a dynamic structure to fit different external environments by adjusting the parameter values of SAIGM. However, the order number of the raw SAIGM model is not optimal, which is an integer. For this, a new SAIGM model with the fractional order accumulating operator (SAIGM_FO) was proposed in this paper. Specifically, the final restored expression of SAIGM_FO was deduced in detail, and the parameter estimation method of SAIGM_FO was studied. After that, the Particle Swarm Optimization algorithm was used to optimize the order number of SAIGM_FO, and some steps were provided. Finally, the SAIGM_FO model was applied to simulate China's electricity consumption from 2001 to 2008 and forecast it during 2009 to 2015, and the mean relative simulation and prediction percentage errors of the new model were only 0.860% and 2.661%, in comparison with the ones obtained from the raw SAIGM model, the GM(1, 1) model with the optimal fractional order accumulating operator and the GM(1, 1) model, which were (1.201%, 5.321%), (1.356%, 3.324%), and (2.013%, 23.944%), respectively. The findings showed both the simulation and the prediction performance of the proposed SAIGM_FO model were the best among the 4 models.     

基于中空多孔金纳米/石墨烯复合纳米材料的葡萄糖氧化酶直接电化学及其生物传感研究

采用溶液相牺牲模板法制备中空多孔金纳米粒子（HPAuNPs）,并将该材料与还原氧化石墨烯（rGO）复合,用于葡萄糖氧化酶（GOx）在玻碳电极（GCE）表面的有效固定,构建GOx/HPAuNPs/rGO/GCE传感界面。利用扫描和透射电镜、X射线光电子能谱、X射线衍射谱、红外光谱及电化学等方法对材料的形貌与结构,GOx的固定化过程,以及传感器的直接电化学和电催化性能进行表征。结果表明,HPAuNPs和rGO的协同作用能有效促进GOx与电极之间的直接电子转移（DET）。基于GOx/HPAuNPs/rGO/GCE对葡萄糖的良好电催化性能,该方法有效实现了对葡萄糖的高灵敏度检测,其电流响应的线性范围为0.05～7.0 mmol/L,检出限（S/N=3）为16μmol/L。该传感器具有良好的选择性、重现性及稳定性,对实际样品血清中血糖的测定结果令人满意,回收率为98.0%～103%,相对标准偏差不大于5.0%。     

Highly Selective Photoelectroreduction of Carbon Dioxide to Ethanol over Graphene/Silicon Carbide Composites

Using sunlight to produce valuable chemicals and fuels from carbon dioxide (CO₂), i.e., artificial photosynthesis (AP) is a promising strategy to achieve solar energy storage and a negative carbon cycle. However, selective synthesis of C₂ compounds with a high CO₂ conversion rate remains challenging for current AP technologies. We performed CO₂ photoelectroreduction over a graphene/silicon carbide (SiC) catalyst under simulated solar irradiation with ethanol (C₂H₅OH) selectivity of>99 % and a CO₂ conversion rate of up to 17.1 mmol g_cat⁻¹ h⁻¹ with sustained performance. Experimental and theoretical investigations indicated an optimal interfacial layer to facilitate the transfer of photogenerated electrons from the SiC substrate to the few-layer graphene overlayer, which also favored an efficient CO₂ to C₂H₅OH conversion pathway.     

Solvent-Free Heterogeneous Catalytic Hydrogenation of Polyesters to Diols

The utilization of carbon resources stored in plastic polymers through chemical recycling and upcycling is a promising approach for mitigating plastic waste. However, most current methods for upcycling suffer from limited selectivity towards a specific valuable product, particularly when attempting full conversion of the plastic. We present a highly selective reaction route for transforming polylactic acid (PLA) into 1,2-propanediol utilizing a Zn-modified Cu catalyst. This reaction exhibits excellent reactivity (0.65 g g_cat⁻¹ h⁻¹) and selectivity (99.5 %) towards 1,2-propanediol, and most importantly, can be performed in a solvent-free mode. Significantly, the overall solvent-free reaction is an atom-economical reaction with all the atoms in reactants (PLA and H₂) fixed into the final product (1,2-propanediol), eliminating the need for a separation process. This method provides an innovative and economically viable solution for upgrading polyesters to produce high-purity products under mild conditions with optimal atom utilization.     

Peripherally Heavy-Atom-Decorated Strategy Towards High-Performance Pure Green Electroluminescence with External Quantum Efficiency over 40 %

Heavy-atom integration into thermally activated delayed fluorescence (TADF) molecule could significantly promote the reverse intersystem crossing (RISC) process. However, simultaneously achieving high efficiency, small roll-off, narrowband emission and good operational lifetime remains a big challenge for the corresponding organic light-emitting diodes (OLEDs). Herein, we report a pure green multi-resonance TADF molecule BN-STO by introducing a peripheral heavy atom selenium onto the parent BN-Cz molecule. The organic light-emitting diode device based on BN-STO exhibited state-of-the-art performance with a maximum external quantum efficiency (EQE) of 40.1 %, power efficiency (PE) of 176.9 lm W⁻¹, well-suppressed efficiency roll-off and pure green gamut. This work reveals a feasible strategy to reach a balance between fast RISC process and narrow full width at half maximum (FWHM) of MR-TADF by heavy atom effect.     

Sulfur-Containing Foldamer-Based Artificial Lithium Channels

Unlike many other biologically relevant ions (Na⁺, K⁺, Ca²⁺, Cl⁻, etc) and protons, whose cellular concentrations are closely regulated by highly selective channel proteins, Li⁺ ion is unusual in that its concentration is well tolerated over many orders of magnitude and that no lithium-specific channel proteins have so far been identified. While one naturally evolved primary pathway for Li⁺ ions to traverse across the cell membrane is through sodium channels by competing with Na⁺ ions, highly sought-after artificial lithium-transporting channels remain a major challenge to develop. Here we show that sulfur-containing organic nanotubes derived from intramolecularly H-bonded helically folded aromatic foldamers of 3.6 Å in hollow cavity diameter could facilitate highly selective and efficient transmembrane transport of Li⁺ ions, with high transport selectivity factors of 15.3 and 19.9 over Na⁺ and K⁺ ions, respectively.     

Rhodium-Catalyzed Regio- and Diastereoselective [3+2] Cycloaddition of gem-Difluorinated Cyclopropanes with Internal Olefins

Direct synthesis of gem-difluorinated carbocyclic molecules represents a longstanding challenge in organic chemistry. Herein, a Rh-catalyzed [3+2] cycloaddition reaction between readily available gem-difluorinated cyclopropanes (gem-DFCPs) and internal olefins has been developed, enabling the efficient synthesis of gem-difluorinated cyclopentanes with good functional group compatibility, excellent regioselectivity and good diastereoselectivity. The resulting gem-difluorinated products can undergo downstream transformations to access various mono-fluorinated cyclopentenes and cyclopentanes. This reaction demonstrates the use of gem-DFCPs as a type of “CF₂” C3 synthon for cycloaddition under transition metal catalysis, which provides potential strategy for synthesizing other gem-difluorinated carbocyclic molecules.     

Programmable and Self-Healable Liquid Crystal Elastomer Actuators Based on Halogen Bonding

Shape-changing polymeric materials have gained significant attention in the field of bioinspired soft robotics. However, challenges remain in versatilizing the shape-morphing process to suit different tasks and environments, and in designing systems that combine reversible actuation and self-healing ability. Here, we report halogen-bonded liquid crystal elastomers (LCEs) that can be arbitrarily shape-programmed and that self-heal under mild thermal or photothermal stimulation. We incorporate halogen-bond-donating diiodotetrafluorobenzene molecules as dynamic supramolecular crosslinks into the LCEs and show that these relatively weak crosslinks are pertinent for their mechanical programming and self-healing. Utilizing the halogen-bonded LCEs, we demonstrate proof-of-concept soft robotic motions such as crawling and rolling with programmed velocities. Our results showcase halogen bonding as a promising, yet unexplored tool for the preparation of smart supramolecular constructs for the development of advanced soft actuators.     

Promoting CO2 Electroreduction to Multi-Carbon Products by Hydrophobicity-Induced Electro-Kinetic Retardation

Advancing the performance of the Cu-catalyzed electrochemical CO₂ reduction reaction (CO₂RR) is crucial for its practical applications. Still, the wettable pristine Cu surface often suffers from low exposure to CO₂, reducing the Faradaic efficiencies (FEs) and current densities for multi-carbon (C₂₊) products. Recent studies have proposed that increasing surface availability for CO₂ by cation-exchange ionomers can enhance the C₂₊ product formation rates. However, due to the rapid formation and consumption of *CO, such promotion in reaction kinetics can shorten the residence of *CO whose adsorption determines C₂₊ selectivity, and thus the resulting C₂₊ FEs remain low. Herein, we discover that the electro-kinetic retardation caused by the strong hydrophobicity of quaternary ammonium group-functionalized polynorbornene ionomers can greatly prolong the *CO residence on Cu. This unconventional electro-kinetic effect is demonstrated by the increased Tafel slopes and the decreased sensitivity of *CO coverage change to potentials. As a result, the strongly hydrophobic Cu electrodes exhibit C₂₊ Faradaic efficiencies of ≈90 % at a partial current density of 223 mA cm⁻², more than twice of bare or hydrophilic Cu surfaces.     

Triple-function Hydrated Eutectic Electrolyte for Enhanced Aqueous Zinc Batteries

Aqueous rechargeable zinc-ion batteries (ARZBs) are impeded by the mutual problems of unstable cathode, electrolyte parasitic reactions, and dendritic growth of zinc (Zn) anode. Herein, a triple-functional strategy by introducing the tetramethylene sulfone (TMS) to form a hydrated eutectic electrolyte is reported to ameliorate these issues. The activity of H₂O is inhibited by reconstructing hydrogen bonds due to the strong interaction between TMS and H₂O. Meanwhile, the preferentially adsorbed TMS on the Zn surface increases the thickness of double electric layer (EDL) structure, which provides a shielding buffer layer to suppress dendrite growth. Interestingly, TMS modulates the primary solvation shell of Zn²⁺ ultimately to achieve a novel solvent co-intercalation ((Zn-TMS)²⁺) mechanism, and the intercalated TMS works as a “pillar” that provides more zincophilic sites and stabilizes the structure of cathode (NH₄V₄O₁₀, (NVO)). Consequently, the Zn||NVO battery exhibits a remarkably high specific capacity of 515.6 mAh g⁻¹ at a low current density of 0.2 A g⁻¹ for over 40 days. This multi-functional electrolytes and solvent co-intercalation mechanism will significantly propel the practical development of aqueous batteries.