摘要：结合了三维结构和亲锌物种的集流体构筑策略被认为是构建高稳定锌金属负极的有效方法.然而,高昂的成本和复杂的制备工艺阻碍了其实际应用.本文通过在有均匀Cu^(2+)锚定的碳布集流体(ACC-600@Cu^(2+))上沉积锌,合理设计了一种稳定的三维锌金属复合阳极(Zn@ACC-600@Cu^(2+)).在锌成核过程中,Cu^(2+)原位还原为金属Cu,然后随着锌的进一步沉积,碳布表面逐渐形成均匀的亲锌的Cu-Zn合金界面层.密度泛函理论计算和实验观察表明,Cu-Zn合金界面不仅可以作为锌离子的亲锌沉积点,而且可以提高导电率,使电场和锌离子通量均匀化.因此,ACC-600@Cu^(2+)集流体可以实现高的镀锌/剥离可逆性,并在15.8 mV的极化电压下稳定循环410 h以上.作为概念验证,我们组装的Zn@ACC-600@Cu^(2+)‖MnO_(2)全电池具有良好的电池倍率性能,与原始碳布相比,其比容量显著提高至110 mA h g^(-1).本文提出的原位还原策略为三维锌金属复合负极的设计提供了一种简便且低成本的方法,促进了无枝晶和高稳定锌金属电池的发展.

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：Efficient multi-resonance thermally activated delayed fluorescence(MR-TADF)materials hold significant potential for applications in organic light-emitting diodes(OLEDs)and ultra-high-definition ***,the stringent synthesis conditions and low yields typically associated with these materials pose substantial challenges for their practical *** this study,we introduce an innovative strategy that involves peripheral modification with sulfur and selenium atoms for two materials,CFDBNS and *** approach enables a directed one-shot borylation process,achieving synthesis yields of 66%and 25%,respectively,while also enhancing reverse intersystem crossing *** emitters exhibit ultra-narrowband sky-blue emissions centered around 474 nm,with full width at half maximum(FWHM)values as narrow as 19 nm in dilute toluene solutions,along with high photoluminescence quantum yields of 98%and 99%in doped films,*** OLEDs based on CFDBNS and CFDBNSe display sky-blue emissions with peaks at 476 and 477 nm and exceptionally slender FWHM values of 23 ***,the devices demonstrate remarkable performances,achieving maximum external quantum efficiencies of 24.1%and 27.2%.This work presents a novel and straightforward approach for the incorporation of heavy atoms,facilitating the rapid construction of efficient MR-TADF materials for OLEDs.

摘要：The sluggish kinetics of oxygen reduction reaction(ORR)hinders the commercialization of Zn‐air batteries(ZABs).Manipulating the electronic structure of electrocatalysts to optimize the adsorption energy of oxygen‐containing intermediates during the 4e–ORR offers a practical route toward improving ORR ***,we designed a novel ORR electrocatalyst containing Co single atoms and nanoparticles supported by carbon dots‐derived carbon nanoflowers(Co SAs/NPs CNF).Co SAs/NPs CNF possessed a very high ORR activity(E_(1/2) of the Co SAs/NPs CNF catalyst is 0.83 V(***)),and outstanding catalytic performance and stability when used as the air‐electrode catalyst in rechargeable ZABs(152.32 mW cm^(-2),1000.58 mWh gZn^(–1),and over 1300 cycles at a current density of 5 mA cm^(-2)).The Co SAs and Co NPs cooperated to improve electron and proton transfer processes during *** calculations revealed that the presence of adjacent Co NPs optimized the electronic structure of the isolated Co‐N_(4) sites,significantly lowering the energy barriers for the rate‐determining step in ORR(adsorption of*OOH)and thereby delivering outstanding ORR *** work reveals that the combination of supported single‐atom sites and metal nanoparticles can be highly beneficial for ORR electrocatalysis,outperforming catalysts containing only Co SAs or Co NPs.

摘要：Cobalt nanoparticles(NPs)catalysts are extensively used in heterogeneous catalytic reactions,and the addition of alkali metal promoters is a common method to modulate the catalytic performance because the catalyst's surface structures and morphologies are sensitive to the addition of ***,the underlying modulation trend remains ***,the adsorption of alkali metal promoters(Na and K)on the surfaces of face-centered-cubic(FCC)and hexagonal-closest packed(HCP)polymorphous cobalt was systematically investigated using density functional ***,the effect of alkali promoters on surface energies and nanoparticle morphologies was revealed on the basis of Wulff *** FCC-Co,the exposed area of the(111)facet in the nanoparticle increases with the adsorption coverage of alkali metal ***,the(311),(110),and(100)facets would disappear under the higher adsorption coverage of alkali *** HCPCo,the Wulff morphology is dominated by the(0001)and(1011)facets and is independent of the alkali metal adsorption *** work provides insights into morphology modulation by alkali metal promoters for the rational design and synthesis of cobalt-based nanomaterials with desired facets and morphologies.

摘要：Methanol to olefins(MTO)reaction as an important non-oil route to produce light olefins has been industrialized,and received over 80% ethylene plus propylene ***,to achieve high single ethylene or propylene selectivity towards the fluctuated market demand is still full of ***-pore SAPO-14 molecular sieve is a rare MTO catalyst exhibiting extra-high propylene *** provides us a valuable clue for further understanding of the relationship between molecular sieve structure and MTO catalytic *** this work,a seconds-level sampling fixed-bed reactor was used to capture real-time product distributions,which help to achieve more selectivity data in response to very short catalytic life of *** in product distribution,especially during the low activity stage,reflect valuable information on the reaction *** with in situ diffuse reflectance infrared Fourier-transform spectroscopy,in situ ultraviolet Raman measurements and ^(12)C/^(13)C isotopic switch experiments,a reaction pathway evolution from dual cycle to olefins-based cycle dominant was *** addition,the deactivation behaviors of SAPO-14 were also investigated,which revealed that polymethylbenzenes have been the deactivated species in such a *** work provides helpful hints on the development of characteristic methanol to propylene(MTP)catalysts.

摘要：Carbon dioxide as a notorious greenhouse gas triggers severe global warming which is threatening the balance of ecosystem. In this respect, effectively capturing and transforming CO_(2)into value-added chemicals are essential but still challenging tasks. As a kind of emerging crystalline porous material, covalent organic frameworks(COFs) have been demonstrated to be able to adsorb gases and function as catalysts to facilitate chemical transformations. Herein, we report an imine-linked, cobalt sandwich complex-based COF(Co-BD-COF) with high crystallinity and large surface ***-BD-COF can efficiently catalyze the transformation of CO_(2)into cyclic carbonates due to abundant metal sites and high porosity. In addition, Co-BD-COF exhibits high catalytic selectivity toward small ethylene oxide derivatives in cycloaddition reaction due to the large steric hindrance around the cobalt complexes rendered by the peripheral phenyl *** new metal sandwich-type building block provides a new strategy for improving catalytic selectivity of COFs.

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：Photocatalytic water splitting with simultaneous degradation of organic pollutants is an effective strategy to alleviate the increasingly serious energy and environmental ***,the photocatalytic activity is restricted by the high charge recombination rate and limited sunlight ***,black phosphorus(BP)with a broad sunlight response range was utilized as a photosensitizer to enhance the photocatalytic performance of the Au/carbon nitride(CN)*** as-prepared BP/Au/CN exhibited a significantly enhanced H_(2) generation rate of 1400.8µmol h^(−1) g^(−1) under UV-vis light irradiation,which is almost 70 times higher than that of bare CN and BP/CN and 2 folds higher than that of the Au/CN ***,the optimal BP/Au/CN sample presented a waste-to-hydrogen production rate of 195.8µmol h^(−1) g^(−1) with the degradation of bisphenol A,verifying the synergistic effect of the ternary *** photocatalytic mechanism was systematically studied by the combination of experiments and theoretical *** improved photocatalytic performance was derived from the overall sunlight absorption ability of BP,effective electron transfer media and plasmonic character of Au nanoparticles,as well as the matched work function and strong interaction of the three components.A unidirectional electron transfer from BP to Au and then to CN was established,which effectively improved the charge transfer capability,resulting from the appropriate Ohmic contact of Au and BP and the Schottky barrier constructed in Au/CN hybrid.

摘要：The typical Haber technical process for industrial NH_(3)production involves plenty of energy-consumption and large quantities of greenhouse gas *** contrast,electrochemical N_(2)reduction proffers environment-friendly and energy-efficient avenues to synthesize NH_(3)at mild conditions but demands efficient electrocatalysts for the N_(2)reduction reaction(NRR).Herein we report for the first time that commercial indium-tin oxide glass(ITO/G)can be used as a catalyst electrode toward artificial N_(2)fixation,as it demonstrates excellent selectivity at mild *** ITO/G delivers excellent NRR performance with a NH_(3)yield of 1.06×10^(-10) mol s^(-1) cm^(-2) and a faradaic efficiency of 6.17%at-0.40 V versus the reversible hydrogen electrode(RHE)in 0.5 M ***,the ITO/G also possesses good electrochemical stability and ***,the possible reaction mechanism for the NRR on the ITO catalysts was explored using first-principles calculations.