摘要：混合基质膜(MMMs)将多孔材料与聚合物基质相结合,因其互补特性和协同激活已经在气体分离领域引起了相当大的研究兴趣。多孔材料的可塑性和多样性赋予MMMs可延伸的功能和出色的分离性能。为了发挥MMMs的全部潜力,研究人员关注多孔填料与聚合物基质的合理匹配,以实现这些材料之间界面的增强相容性。在本文中,我们重点介绍采用不同策略将金属-有机框架(MOFs)和金属-有机笼(MOCs)与聚合物基质相结合制备MMMs的最新进展。文中进一步讨论未来MMMs发展所面临的机遇和挑战,并旨在通过合理的材料设计和选择推动MMMs的制备。

摘要：Cocrystal has been discovered and studied for more than 170 years since 1844, while the applications to optoelectronics only begin in the last decade. Several general questions that chemists and materials scientists currently seek to answer are: can we design and control the molecular self-assembly and cocrystal growth, what’s the packing-property correlations, as well as how can we improve device parameters for real applications in industry. In this contribution, we review our and other groups’ recent advances in the cocrystal research field sequentially including:(1) nucleation and growth mechanisms for selective preparation of cocrystals with different donor/acceptor ratio and morphology;(2) charge transport and electronic devices, particularly field-effect transistor(FET) and photo-response device. We discuss the in-situ single crystal device fabrication method, ambipolar charge transport, and molecular packingcharge separation correlation;(3) photonic and optical property, focusing on optical waveguide, photonic logic computation, and nonlinear optics(NLO). We present unusual optical properties revealed by advanced instruments and general structure-function relations for future study. Importantly, the extensive investigations described herein yield in-depth and detailed understandings of molecular cocrystals,and show that such bi-component material systems together with the developed instrument measurement methodologies have the potential to initiate unconventional electronic and photonic science and technology.

摘要：Designing highly selective and efficient singleatom electrocatalysts is essential for ammonia production under ambient conditions. This paper describes a density functional theory study on exploring the performance trends of transition metal complexes with P-based ligands in nitrogen reduction reaction(NRR) and further develops a design principle for high-performance single-atom catalysts(SACs)of NRR. Among the explored catalysts, W@BP(0.40 eV),Ta@BP(0.47 eV), and Nb@BP(0.53 eV) are identified as remarkable candidates with low free energy change in the potential-limiting step, high stability and high electrical conductivity for NRR. It is worth noting that almost all SACs with P-based ligands exhibit high NRR selectivity, due to the fact that they adsorb *N_(2) more strongly than *H. The adsorption free energy of *N_(2) H can be considered as a descriptor for the intrinsic activity trends in NRR. Furthermore, by constructing a volcano plot of the activity against the electronic charge on metal centers, it is demonstrated that the metal center with a moderate amount of positive charge can promote the catalytic performance of NRR.

摘要：The rational design and synthesis of hybrid-type electrode nanomaterials are significant for their diverse applications,including their potential usage as high-efficiency nanoarchitectures for supercapacitors(SCs)as a class of promising energy-storage systems for powering next-generation electric vehicles and electronic ***,we reported a facile and controllable synthesis of core-shell Ni_(3)S_(2)@NiWO_(4)nanoarrays to fabricate a freestanding electrode for hybrid ***,the as-prepared freestanding Ni_(3)S_(2)@NiWO_(4)electrode presents an ultrahigh areal capacity of 2032μA h cm^(-2)at 5 mA cm^(-2),and a capacity retention of 63.6%even when the current density increased up to 50 mA cm^(-2).Remarkably,the Ni_(3)S_(2)@NiWO_(4)nanoarraybased hybrid SC delivers a maximum energy density of 1.283 mW h cm^(-2)at 3.128 mW cm^(-2)and a maximum power density of 41.105 mW cm^(-2)at 0.753 mW h cm^(-2).Furthermore,the hybrid SC exhibits a capacity retention of 89.6%even after continuous 10,000 cycles,proving its superior *** study provides a facile pathway to rationally design a variety of core-shell metal nanostructures for high-performance energy storage devices.

摘要：The phenomenon that different molecular packing modes in aggregates result in different optical properties has attracted intense attention,since it can provide useful information to establish the relationship between the micro-and *** this paper,DBTDO-DMAC was designed with 9,10-dihydro-9,9-dimethylacridine(DMAC)as electron ***-DPA and DBTDO-Cz were designed for comparison,which adopted diphenylamine(DPA)with twisted structure and carbazole(Cz)with planar structure as donors,*** expected,two polymorphs(Crystal G and Crystal Y)of DBTDO-DMAC were obtained and exhibited distinct *** G originating from planar conformation exhibited mechanochromism(MC)phenomenon and the emission color changed from green to yellow with a redshift of 35 nm after ***,Crystal Y with folded conformation displayed obvious room-temperature phosphorescence(RTP)with yellow *** single crystal analyses,powder X-ray diffraction and theoretical calculation reveal that the different emissive behaviors are highly related to the molecular conformation and packing *** successful adjustment of molecular conformation provides some guidance in the design of other MC and/or RTP luminogens,broadens the molecule family with the tunable molecular conformation and opens up a new avenue for exploring possible adjustment of molecular packing in aggregates.

摘要：甲烷化学链部分氧化(CL-POM)是一种有前景的合成气生产技术,具有高选择性和低爆炸风险的优势.然而,开发性能优异、可持续释氧的金属载氧体仍然面临挑战.为此,本研究设计了一种复合载氧体(LaFeO_(3-δ)/Ca_(1-η)Sr_(η)MnO_(3)),通过调控Ca_(1-η)Sr_(η)MnO_(3)的氧扩散来维持LaFeO_(3-δ)(121)缺陷表面的活性结构,从而提升了CL-POM的活性和选择性.理论计算结果表明,甲烷在LaFeO_(3-δ)(121)缺陷表面上的反应活性位点主要是Fe-O_(4)(O_(V))和Fe-O_(3)(O_(V))_(2),它们表现出相近的反应能垒(ΔG_(a)=1.44和1.40 eV).氧扩散系数和表面反应速率常数分别由体相氧迁移能垒和表面反应能垒确定,进而计算得到体相氧扩散和表面反应的速率,用以评估两者的匹配程度.最后,本研究证实了LaFeO_(3-δ)/Ca_(0.75)-Sr_(0.25)MnO_(3)是一种有潜力的CL-POM载氧体,其能够实现体相氧扩散速率与表面氧消耗速率的合理匹配,并有效地抑制不利的相变过程.

摘要：The Pt-based catalyst tends to be poisoned by carbon monoxide(CO)-like intermediates produced in fuel cell reactions,which seriously deteriorates its catalytic ***,noble metal Au with the capacity of resistance to CO-like intermediates poisoning was employed to construct multi-element Pt-based *** trimetallic NiPtAu hollow nanocrystals(HNCs)with different surface Au contents were synthesized to explore the role of Au in electrocatalysis for alkaline methanol oxidation reaction(MOR).The trimetallic NiPtAu-SRAu HNCs catalyst with the relative rich Au content(15.17 at%)on surface exhibits a much lower CO oxidation peak potential than the other HNCs counterpart and 20 wt%Pt/C,which indicates the more exceptional CO-resisting ***,the MOR specific activity of NiPtAu-SRAu HNCs(31.52 mA cm^−2)is 7 times higher than that of 20wt%Pt/C(4.50 mA cm^−2).This enhancement in catalytic activity as well as anti-CO poisoning capability for NiPtAu-SRAu HNCs can be mainly ascribed to the weakened CO adsorption due to the exposure of Au atoms on NiPt surface evidenced by the experimental data and density functional theory *** study not only investigates the role of Au in MOR catalysis but also could be helpful for designing and optimizing the electrocatalysts for high-active and robust fuel cell applications.

摘要：The overall water splitting for hydrogen production is an effective strategy to resolve the environmental and energy crisis. Here, we report a facile approach to synthesize the Ir-based multimetallic, hierarchical, double-coreshelled architecture(HCSA) assisted by oil bath reaction for boosting overall water splitting in acidic environment. The Ir Ni Cu HCSA shows superior electrocatalytic activity for hydrogen evolution reaction(HER) and oxygen evolution reaction(OER), which are comparable to commercial Pt/C and better than IrO2. The Ir Ni Cu HCSA exhibits remarkably catalytic efficiency as bifunctional catalyst for overall water splitting where a low cell voltage of 1.53 V is enough to drive a current density of 10 mA cm^-2 and maintains stable for at least 20 h. The presented work for the design and synthesis of novel Ir-based multimetallic architecture paves the way for highperformance overall water splitting catalysis.

摘要：Photonic synaptic transistors are promising neuromorphic computing systems that are expected to circumvent the intrinsic limitations of von Neumann-based *** design and construction of photonic synaptic transistors with a facile fabrication process and highefficiency information processing ability are highly desired,while it remains a tremendous ***,a new approach based on spin coating of a blend of CsPbBr_(3) perovskite quantum dot(QD)and PDVT-10 conjugated polymer is reported for the fabrication of photonic synaptic *** combination of flat surface,outstanding optical absorption,and remarkable charge transporting performance contributes to high-efficiency photon-to-electron conversion for such perovskite-based ***-performance photonic synaptic transistors are thus fabricated with essential synaptic functionalities,including excitatory postsynaptic current(EPSC),paired-pulse facilitation(PPF),and long-term *** utilizing the photonic potentiation and electrical depression features,perovskite-based photonic synaptic transistors are also explored for neuromorphic computing simulations,showing high pattern recognition accuracy of up to 89.98%,which is one of the best values reported so far for synaptic transistors used in pattern *** work provides an effective and convenient pathway for fabricating perovskite-based neuromorphic systems with high pattern recognition accuracy.

摘要：Sluggish water dissociation kinetics severely limits the rate of alkaline electrocatalytic hydrogen evolution reaction(HER).Therefore,finding highly active electrocatalysts and clarifying the mechanism of water dissociation are challenging but *** this study,we report an integrated nanoporous nickel(np-Ni)catalyst with high alkaline HER performance and the origin of the corresponding enhanced catalytic *** 1 mol L^(-1) KOH solution,this np-Ni electrode shows an HER overpotential of 20 mV at 10 mA cm^(-2),along with fast water dissociation *** excellent performance is not only attributed to the large surface area provided by the three-dimensional interconnected conductive network but also from the enhanced intrinsic activity induced by the unique surface *** studies reveal that the types of oxygen species that naturally form on the Ni surface play a key role in water ***,when the lattice oxygen almost disappears,the Ni surface terminates with_(ads)orbed oxygen(O_(ads)),exhibiting the fastest water dissociation *** functional theory calculation suggests that when O_(ads)acts as the surface termination of Ni metal,the orientation and configuration of polar water molecules are strongly affected by O_(ads).Finally,the H–OH bond of interfacial water molecules is effectively activated in a manner similar to hydrogen *** work not only identifies a high-performance and low-cost electrocatalyst but also provides new insights into the chemical processes underlying water dissociation,thus benefiting the rational design of electrocatalysts.