The properties of metal materials can be greatly enriched by including various elements to generate alloys. The galvanic replacement represents a classical method for the preparation of both bulk-and nanoalloy materials. The difference of the electrochemical potential between the two metals acts as the driving force for the galvanic replacement reaction. However, this classical rule partially fails at the ultrasmall size scale, for that novel chemistry emerges by the decrease of the size of materials down to less than 3 nm due to the strong quantum effect. In this Account, we discuss an emerging topic of nanochemistry, the metal exchange in atomically precise ultrasmall (<3 nm) metal nanoparticles (or nanoclusters). The metal exchange method uses different types of metal sources (e.g., AuBrPPh 3 or AgSR complexes) to react with templating metal nanoclusters (e.g., Au 25 (SR) 18 − ), and finally alloy nanoclusters are produced. We demonstrate that the metal exchange reaction between metal nanoclusters and metal complexes does not follow the classical metal activity sequence (i.e., Fe > Cd > Co > Ni > Pb > Cu > Hg > Ag > Pd > Pt > Au) and such metal exchange reactions in the nanocluster range is, to a large extent, related with the electron shell closing and the structural stability of nanoclusters.In the subsequent sections, we present effective control over the number, position, and distribution of the dopants. The shape and structure of the final alloy products can be tailored by recently developed metal exchange methods. More importantly, modulation and enhancement of the properties of NCs through metal exchange are realized. For example, the largely increased quantum yield and the significantly improved catalytic activity. In addition, we shall also discuss the real-time characterization of the metal exchange reaction by the combination of UV−vis absorption spectroscopy, high resolution electrospray ionization mass spectrometry (ESI-MS), matrix assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS), and single crystal X-ray diffraction (SC-XRD). By controlling the charge of the templating metal nanoclusters and the different types of metal complexes, the driving force of metal exchange has been studied, which is considered to be the thermodynamics rather than the electrochemical potential. In summary, the metal exchange reactions in the ultrasmall nanocluster range are totally different compared with the case of larger-sized metal nanoparticles. Depending on this novel method, atomically precise alloy nanoclusters can be prepared by reacting the nanocluster composed of inert metal (such as Au) with complexes of high-activity metals (e.g., Cd/Hg/Cu/Ag). We anticipate that future research on the metal exchange will contribute to the fundamental understanding of reaction behavior of metal atoms in ultrasmall nanoclusters and to the design of alloy nanoclusters with enhanced properties.

Mesoporous spinel nickel cobaltite (NiCo2O4) nanostructures were synthesized via a facile chemical deposition method coupled with a simple post-annealing process. The physicochemical properties were characterized via X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS) and nitrogen sorption measurements. The electrocatalytic performances were investigated by cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) tests. The obtained NiCo₂O₄ materials exhibit typical agglomerate mesoporous nanostructures with a large surface area (190.1 m(2) g(-1)) and high mesopore volume (0.943 cm(3) g(-1)). Remarkably, the NiCo₂O₄ shows much higher catalytic activity, lower overpotential, better stability and greater tolerance towards urea electro-oxidation compared to those of cobalt oxide (Co₃O₄) synthesized by the same procedure. The NiCo₂O₄ electrode delivers a current density of 136 mA cm(-2) mg(-1) at 0.7 V (vs. Hg/HgO) in 1 M KOH and 0.33 M urea electrolytes accompanied with a desirable stability. The impressive electrocatalytic activity is largely ascribed to the high intrinsic electronic conductivity, superior mesoporous nanostructures and rich surface Ni active species of the NiCo₂O₄ materials, which can largely boost the interfacial electroactive sites and charge transfer rates for urea electro-oxidation, indicating promising applications in future wastewater remediation, hydrogen production and fuel cells.

The lithium-based energy storage technology is currently being considered for electric automotive industry and even electric grid storage. However, the hungry demand for vast energy sources in the modern society will conflict with the shortage of lithium resources on the earth. The first alternative choice may be sodium-related materials. Herein, we propose an electric energy storage system (sodium-ion capacitor) based on porous carbon and sodium titanate nanotubes (Na-TNT, Na(+)-insertion compounds) as positive and negative electrode materials, respectively, in conjunction with Na(+)-containing non-aqueous electrolytes. As a low-voltage (0.1-2 V) sodium insertion nanomaterial, Na-TNT was synthesized via a simple hydrothermal reaction. Compared with bulk sodium titanate, the predominance of Na-TNT is the excellent rate performance, which exactly caters to the need for electrochemical capacitors. The sodium-ion capacitors exhibited desirable energy density and power density (34 Wh kg(-1), 889 W kg(-1)). Furthermore, the sodium-ion capacitors had long cycling life (1000 cycles) and high coulombic efficiency (≈ 98 % after the second cycle). More importantly, the conception of sodium-ion capacitor has been put forward.

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Increases in the molecular length of narrow band gap conjugated chromophores reveal potentially beneficial optical and electronic properties, thermal stabilities, and high power conversion efficiencies when integrated into optoelectronic devices, such as bulk heterojunction organic solar cells. With the objective of providing useful information for understanding the transition from small-sized molecules to polymers, as well as providing a general chemical design platform for extracting relationships between molecular structure and bulk properties, we set out to vary the electron affinity of the molecular backbone. Therefore, a series of donor (D)-acceptor (A) alternating narrow band gap conjugated chromophores were synthesized based on the general molecular frameworks: D(1)-A(1)-D(2)-A(2)-D(2)-A(1)-D(1) and D(1)-A(1)-D(2)-A(2)-D(2)-A(2)-D(2)-A(1)-D(1). When the central electron-accepting moiety (A(2)) was varied or modified, two classes of molecules could be compared. First, we showed that the alteration of one single electron-accepting group, while maintaining the shape of the molecular framework, can effectively impact the optical properties and energy levels of the molecules. DFT ground state structure optimizations show similar "U" shape conformations among these molecules. Second, we examined how the site-specific introduction of fluorine atom(s) modifies the thermal properties in the solid state, while maintaining relatively similar optical and electrochemical features of interest. Structure-property relationship of such molecular systems could be rationally evaluated in the aspects of thermal-responsive molecular organizations in the solid state and dipole moments both in the ground and excited states. The impact of molecular structure on charge carrier mobilities in field effect transistors and the performance of photovoltaic devices were also studied.

A novel solution-processable small molecule, namely, benzo[1,2-b:4,5-b]bis(4,4'-dihexyl-4H-silolo[3,2-b]thiophene-2,2'-diyl)bis(6-fluoro-4-(5'-hexyl-[2,2'-bithiophene]-5-yl)benzo[c][1,2,5]thiadiazole (p-SIDT(FBTTh2)2), was designed and synthesized by utilizing the silaindacenodithiophene (SIDT) framework as the central D(2) donor unit within the D(1)AD(2)AD(1) chromophore configuration. Relative to the widely studied 7,7'-[4,4-bis(2-ethylhexyl)-4H-silolo[3,2-b:4,5-b']dithiophene-2,6-diyl]bis[6-fluoro-4-(5'-hexyl-[2,2'-bithiophene]-5-yl)benzo[c][1,2,5]thiadiazole] (p-DTS(FBTTh2)2), which contains the stronger donor fragment dithienosilole (DTS) as D(2), one finds that p-SIDT(FBTTh2)2 exhibits a wider band gap and can be used to fabricate bulk heterojunction solar cells with higher open circuit voltage (0.91 V). Most remarkably, thin films comprising p-SIDT(FBTTh2)2 can achieve exceptional levels of self-organization directly via solution deposition. For example, high-resolution transmission electron microscopy analysis shows that p-SIDT(FBTTh2)2 spin-cast from chlorobenzene organizes into crystalline domains with lattice planes that extend over length scales on the order of hundreds of nanometers. Such features suggest liquid crystalline properties during the evolution of the film. Moreover, grazing incidence wide-angle X-ray scattering analysis shows a strong tendency for the molecules to exist with a strong "face-on" orientation relative to the substrate plane. Similar structural features, albeit of more restricted dimensions, can be observed within p-SIDT(FBTTh2)2:PC71BM bulk heterojunction thin films when the films are processed with 0.4% diiodooctane (DIO) solvent additive. DIO use also increases the solar cell power conversion efficiencies (PCEs) from 1.7% to 6.4%. Of significance from a practical device fabrication perspective is that, for p-SIDT(FBTTh2)2:PC71BM blends, there is a wide range of compositions (from 20:80 to 70:30 p-SIDT(FBTTh2)2:PC71BM) that provide good photovoltaic response, i.e., PCE = 4-6%, indicating a robust tendency to form the necessary continuous phases for charge carrier collection. Light intensity photocurrent measurements, charge selective diode fabrication, and internal quantum efficiency determinations were carried out to obtain insight into the mechanism of device operation. Inclusion of DIO in the casting solution results in films that exhibit much lower photocurrent dependence on voltage and a concomitant increase in fill factor. At the optimum blend ratio, devices show high charge carrier mobilities, while mismatched hole and electron mobilities in blends with high or low donor content result in reduced fill factors and device performance.

A facile and high-yield approach to the preparation of few-layer graphene (FLG) by electrochemical intercalation exfoliation (EIE) of expanded graphite in sulfuric acid electrolyte is reported. Stage-1 H2SO4-graphite intercalation compound is used as a key intermediate in EIE to realize the efficient exfoliation. The yield of the FLG sheets (<7 layers) with large lateral sizes (tens of microns) is more than 75% relative to the total amount of starting expanded graphite. A low degree of oxygen functionalization existing in the prepared FLG flakes enables them to disperse effectively, which contributes to the film-forming characteristics of the FLG flakes. These electrochemically exfoliated FLG flakes are integrated into several kinds of macroscopic graphene structures. Flexible and freestanding graphene papers made of the FLG flakes retain excellent conductivity (≈24,500 S m(-1)). Three-dimensional (3D) graphene foams with light weight are fabricated from the FLG flakes by the use of Ni foams as self-sacrifice templates. Furthermore, 3D graphene/Ni foams without any binders, which are used as supercapacitor electrodes in aqueous electrolyte, provide the specific capacitance of 113.2 F g(-1) at a current density of 0.5 A g(-1), retaining 90% capacitance after 1000 cycles.

An ideal crystal quality in the grain interior of perovskite polycrystalline films is well recognized; therefore, understanding interfacial impact and the ways to limit interfacial recombination is critical to fabricating highly efficient solar cells. In perovskite solar cells, PbI2 has been used to passivate defects at grain boundaries, yet a systematic PbI2 passivation engineering to boost the high‐performance perovskite solar cells has not been fully explored. Here, a novel device structure comprised of double‐side‐passivated perovskite solar cells (DSPC) is devised through intentionally distributing PbI2 to both the front/rear‐side surfaces and grain boundaries of the formamidinium‐lead‐iodide‐based (FAPbI3‐based) perovskite film. The minority carrier lifetime in double‐side‐passivated perovskite is extended to 1.1 μs with single‐exponential decay using time‐resolved photoluminescence. This result indicates a generic passivation effect of PbI2 on perovskite interfaces, resembling SiO2 passivation in silicon solar cells. Correspondingly, the best photovoltaic device with TiO2‐based planar structure presents a stabilized efficiency of 22%. Moreover, DSPC effectively boosts the limits of open circuit voltages toward a record potential loss of 0.38 V for 1.53 eV‐bandgap perovskites. The architecture of double‐side‐passivated perovskite opens up new opportunities to exceed the efficiency of state‐of‐the‐art perovskite solar cells.