摘要：Herein,two asymmetric hexacyclic fused small molecule acceptors(SMAs),namely BP4F-HU and BP4F-UU,were *** elongated outside chains in the BP4F-UU molecule played a crucial role in optimizing the morphology of blend film,thereby improving charge mobility and reducing energy loss within the corresponding ***,the PM6:BP4F-UU device exhibited a higher open-circuit voltage(V_(oc))of 0.878 V compared to the PM6:BP4F-HU device with a V_(oc)of 0.863 ***,a new wide bandgap SMA named BTP-TA was designed and synthesized as the third component to the PM6:BP4F-UU host binary devices,which showed an ideal complementary absorption spectrum in PM6:BP4F-UU *** addition,BTP-TA can achieve efficient intermolecular energy transfer to BP4F-UU by fluorescence resonance energy transfer(FRET)pathway,due to the good overlap between the photoluminescence(PL)spectrum of BTP-TA and the absorption region of ***,ternary devices with 15wt%BTP-TA exhibits broader photon utilization,optimal blend morphology,and reduced charge recombination compared to the corresponding binary ***,PM6:BP4F-UU:BTP-TA ternary device achieved an optimal power conversion efficiency(PCE)of 17.83%with simultaneously increased V_(oc)of 0.905 V,short-circuit current density(J_(sc))of 26.14 mA/cm^(2),and fill factor(FF)of 75.38%.

摘要：由于银硫簇的不稳定性和有限的刺激响应特性,构建新型的具有光开关性质的银-硫簇基金属有机框架(SCC-MOF)面临着重大挑战.基于此,本文设计并合成了一种新型光致变色的SCC-MOF(Ag_(12)-BMPTC),该材料利用二芳基乙烯配体和银硫簇前驱体通过溶剂缓慢挥发而得到.Ag_(12)-BMPTC在365和500 nm光照射下表现出优异的可逆光响应特性.此外,这种光开关性质为其在信息加密和手性开关方面提供了潜在应用.本研究不仅扩大了SCC-MOF的种类,而且为设计和合成新型光致变色材料提供了新的思路和潜在应用.

摘要：有机共晶,由于其光热转换性质,为光热成像、生物应用和海水淡化等诸多领域带来了希望和活力.然而,有机共晶的光热转换机制尤其缺少详细且深入的理论研究.本研究使用含时密度泛函理论方法探索了激发和去激发过程,并解释了DBTTF-TCNB共晶比其组分单晶具有更高光热转换效率的原因.结果显示,高激发态的高占比促进了非辐射跃迁的发生.基于DBTTF-TCNB共晶中给电子基团和吸电子基团间的电荷转移结果,我们发现给体和受体之间吸引电子的竞争可能会促进光热转换,且给电子基团在共晶结构中也十分重要.这些结果可为光热转换共晶的设计提供理论指导.轨道贡献和电子密度差进一步证明了我们的结论.因此,本研究从量子化学的角度给光热共晶在创新领域的应用提供了理论依据.

摘要：化学取代是有效调节分子电导,产生多通道输运、量子干涉效应和其他机制的关键方法.但分子骨架和侧基之间存在复杂的相互作用,目前仍未被研究清楚.在本工作中,我们结合扫描隧道显微镜裂结实验技术和第一性原理计算方法,深入研究了具有不同σ和π侧基的分子电导.实验结果及理论分析表明,σ侧基的加入引起了分子前线轨道的对称性破缺并加剧了分子内散射,从而导致电导的降低.相反,π侧基引入了额外的电荷传输通道,实现了电荷传输的多通道效应,增加了分子的电导.这些发现为未来分子功能化和分子电子器件的设计提供了坚实的基础.

摘要：缺陷位点的引入可以通过增加对反应中间体的亲和力来提高催化剂的催化能力.纳米材料中存在多种缺陷类型,如阳离子缺陷和阴离子缺陷.不同的缺陷位点对电催化性能的贡献不同.因此,构筑缺陷必须精准、明确,以便于确定最优的缺陷类型,促进电化学反应.在这项工作中,我们以钴空位为例,分别成功合成了二价钴空位(Co3O 4-VCo(II))和三价钴空位(Co_(3)O_(4)-VCo(III))的Co_(3)O_(4).电化学结果表明,钴空位的引入可以显著提高Co_(3)O_(4)的电催化性能.Co_(3)O_(4)-VCo(II)表现出最突出的析氧反应(OER)性能,反应动力学速率最快.X射线光电子能谱分析表明,在OER过程中,VCo(II)的存在可以使CoOOH活性位点快速形成.密度泛函理论计算表明,钴空位的引入使Co_(3)O_(4)拥有类似金属的导电性.VCo(II)的存在使得O p带中心靠近费米能级,自由能势垒降低,电催化剂表面氧交换动力学速率加快,对反应中间体的吸附能最佳,从而表现出优异的电化学性能.本研究为设计高效的富缺陷电催化剂提供了重要指导.

摘要：开发用于宽pH范围内进行全解水的高效稳定电催化剂是当下的研究热点,但也面临着巨大的挑战.我们通过一种新的空间限域策略合成了锚定在氮掺杂碳(NC)框架表面的超小Co_(4)N纳米点(Co_(4)N@NC).该方法的关键在于功能化低共熔溶剂前驱体组分的设计,由于组分间的氢键相互作用,最终使得超小Co_(4)N纳米点锚定在NC框架上.通过该策略合成的Co_(4)N@NC可以在两相界面处形成新的Co–C化学键,新化学键的形成有利于界面处电子快速转移,并优化了反应物种的吸附/脱附能.Co_(4)N@NC在不同pH值下表现出优异的电催化全解水活性,仅需要1.47 V(0.5 mol L^(-1)H_(2)SO_(4)),1.48 V(1.0 mol L^(-1)KOH)和1.61 V(1.0 mol L^(-1)PBS)的电位即可达到10 m A cm^(-2)的电流密度.本工作为合理设计用于不同电解质下稳定运行的电催化剂提供了理论指导.

摘要：The strontium ions extracted from the aqueous phase into 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide(C_2mimNTf2) with dicyclohexyl-18-crown-6(DCH18C6) was stripped effectively by supercritical CO_2(sc-CO_2).Hexafluoroacetylacetone(HFAA)-acetonitrile was found to be an excellent modifier of sc-CO_2 to enhance the stripping *** the orthogonal array design(OAD),OA_(25)(5~5)matrix was employed to optimize the stripping of Sr(Ⅱ) from the DCH 18C6-C_2mimNTf_2 *** of five experimental factors:temperature,pressure,concentration of HFAA,static and dynamic extraction times as well as each factor at five-levels on the stripping of Sr(Ⅱ) were *** effects of these parameters were treated by the analysis of variance(ANOVA).The results showed that Sr(II) could be nearly 100%extracted from the IL phase at 308 K,30 MPa,40 min of dynamic extraction and 60 mmol·L^(-1) HFAA in acetonitrile,***,the stripping mechanism was studied by ESI-MS.

摘要：低容量和低倍率限制了电池型超级电容阳极材料的大规模应用.本文通过构建一种具有半共格异质界面特性的Fe_(2)O_(3)/FeSe_(2)纳米结构作为先进的阳极材料来解决这一瓶颈.系列表征和第一性原理计算表明,这种特殊的异质界面不仅能自发产生较强的内建电场,从而提高电子传递速率和OH^(-)离子的吸附能力;还可使得活性物质与OH^(-)之间发生更多的氧化还原反应,并且使该反应体系更容易进行.基于上述优势,所制备出的阳极材料的最大比容量为199.2 mA h g^(-1)(1 A g^(-1)),并且在10 A g^(-1)下仍能保持105.8 mA h g^(-1),同时,经历5000次循环后,其比容量可维持初始值的90.2%.此外,以Fe_(2)O_(3)/FeSe_(2)作为阳极组装的非对称超级电容器在0.8 kW kg^(-1)时的能量密度为52.55 Wh kg^(-1),即使经历15,000次循环,该器件还能维持初始容量的91.2%.我们的工作为设计大容量和高倍率性能的电池型超级电容器阳极材料提供了一种创新性的策略,有望推动过渡金属化合物在储能系统中的大规模应用.

摘要：A biosensor device, built from graphene nanoribbons （GNRs） with nanopores, was designed and studied by first- principles quantum transport simulation. We have demonstrated the intrinsic transport properties of the device and the effect of different nucleobases on device properties when they are located in the nanopores of GNRs. It was found that the device＇s current changes remarkably with the species of nucleobases, which originates from their different chemical compositions and coupling strengths with GNRs. In addition, our first-principles results clearly reveal that the distinguished ability of a device＇s current depends on the position of the pore to some extent. These results may present a new way to read off the nucleobases sequence of a single-stranded DNA （ssDNA） molecule by such GNRs-based device with designed nanopores

摘要：A series of novel neonicotinoids derivatives 4a―4p was designed and synthesized by introducing the ethylbenzene group into the thiazole ring, their structures were confirmed by IR, 1H NMR and elemental analysis. The crystal structure of compound 4j has been determined by X-ray diffraction analysis.