Polyvinylpyrrolidone regulated synthesis of mesoporous titanium niobium oxide as high-performance anode for lithium-ion batteries.

TiNb2O7 (TNO) as a promising candidate anode for lithium-ion batteries (LIBs) shows obvious advantages in terms of specific capacity and safety, but which undergoes the intrinsic poor electrical and ionic conductivity. Herein, we propose a simple synthesis strategy of mesoporous TNO via a polymeric surfactant-mediated evaporation-induced sol-gel method, using polyvinylpyrrolidone (PVP) with different molecular weights (average Mw: 10000/58000/1300000) as the regulating agent, which greatly affects the lithium storage performance of the as-prepared TNO. The optimized TNO (i.e., PVP of 58000) delivers a high reversible capacity of 303.1 mAh/g at 1 C, with a retention rate of 73.4% (222.5 mAh/g) after 300 cycles. Even at 5 C, a high reversible capacity of 185.6 mAh/g can be achieved, with a retention rate of 72.3% after 1000 cycles. The superior lithium storage behavior is attributed to the fine mesoporous framework consisting of interconnected TNO nanocrystallites with high specific surface area and high mesoporosity, which greatly increases the active sites, improves the Li+ diffusion kinetics and alleviates volume fluctuation induced by the repetitive Li+ insertion-extraction processes.

A MoSe2/N-doped hollow carbon sphere host for rechargeable Na-Se batteries.

Sodium-selenium (Na-Se) batteries are promising alternatives to lithium-ion batteries for energy storage systems owing to their high energy density and natural abundance of Na resources. However, their drawbacks of low Se loading, dissolution of intermediate sodium polyselenides in the electrolyte and volumetric expansion of Se impede their real applications. To address these issues, herein, we report a multifunctional Se host with MoSe2 nanosheets coupled with nitrogen-doped porous carbon hollow spheres for the first time. The N-doped hollow carbon sphere structure could provide a large space for Se loading (Se content up to 72 wt%) and accommodate the volume expansion of Se species upon cycling. MoSe2 was chosen as a polar coupling component for the carbon matrix, owing to its low conversion reaction voltage. Based on density functional theory (DFT) calculations, the MoSe2 nanosheets coupled with hollow spheres could enhance the adsorption energy of the host to polyselenides chemically, which benefits the immobilization of polyselenides. Therefore, as a cathode for Na-Se batteries, the as-prepared composite exhibits excellent energy storage performance with long cycling life and superior rate performance. Our study of introducing transition metal selenides into Na-Se batteries may stimulate the designing of diverse Se-based cathodes.

MOF-Derived CoS2/N-Doped Carbon Composite to Induce Short-Chain Sulfur Molecule Generation for Enhanced Sodium-Sulfur Battery Performance.

Dissolution of intermediate sodium polysulfides (Na2Sx; 4≤x≤8) is a crucial obstacle for the development of room-temperature sodium-sulfur (Na-S) batteries. One promising strategy to avoid this issue is to load short-chain sulfur (S2-4), which could prohibit the generation of soluble polysulfides during the sodiation process. Herein, unlike in the previous reported cases where short-chain sulfur was stored by confinement within a small-pore-size (≤0.5 nm) carbon host, we report a new strategy to generate short-chain sulfur in larger pores (>0.5 nm) by the synergistic catalytic effect of CoS2 and appropriate pore size. Based on density functional theory calculations, we predict that CoS2 can serve as a catalyst to weaken the S-S bond in the S8 ring structure, facilitating the formation of short-chain sulfur molecules. By experimentally tuning the pore size of the CoS2-based hosts and comparing their performances as cathodes in Na-S and Li-S batteries, we conclude that such a catalytic effect depends on the proximity of sulfur to CoS2. This avoids the generation of soluble polysulfides and results in superior electrochemical properties of the composite materials introduced here for Na-S batteries. As a result, the optimized CoS2/N-doped carbon/S electrode showed excellent electrochemical performance with high reversible specific capacities of 488 mA h g-1 (962 mA h g(s)-1) after 100 cycles (0.1 A g-1) and 403 mA h g-1 after 1000 cycles (1 A g-1) with a superior rate performance (262 mA h g-1 at 5.0 A g-1).

Selenizing CoMoO4 nanoparticles within electrospun carbon nanofibers towards enhanced sodium storage performance.

Transition metal oxides/selenides as anodes for sodium-ion batteries (SIBs) suffer from the insufficient conductivity and large volumetric expansion, which leads to the poor electrochemical performance. To address these issues, we herein demonstrate a facile selenization method to enhance the sodium storage capability of CoMoO4 nanoparticles which are encapsulated into the electrospun carbon nanofibers (CMO@carbon for short). The partially and fully selenized CoMoO4 within carbon nanofibers (denote as CMOS@carbon and CMS@carbon, respectively) can be readily obtained by controlling the annealing temperature (at 400 and 600 °C, correspondingly). When examined as anode materials for SIBs, the CMOS@carbon nanofibers display an outstanding electrochemical performance with a higher reversible capacity of 396 mA h g-1 after 200 cycles at 0.2 A g-1 and a high-rate capacity of 365 mA h g-1 at 2 A g-1, as compared with the CMO@carbon and CMS@carbon counterparts. The enhanced sodium storage performance of the CMOS@carbon can be owing to the partial selenization of the CoMoO4 nanoparticles which are rooted into the porous electrospun carbon nanofibers, thus endowing them with superior ionic/electronic charge transfer efficiencies and a cushion against the electrode pulverization during cycling. Moreover, this work proposed a useful strategy to enhance the sodium storage performance of metal oxides via controlled selenization, which is promising for exploiting the advanced anode materials for SIBs.

Hierarchical CoS2/N-Doped Carbon@MoS2 Nanosheets with Enhanced Sodium Storage Performance.

We introduce a hierarchical nanostructure of CoS2/N-doped carbon@MoS2 comprising two transition-metal sulfides CoS2 and MoS2, with enhanced sodium storage performance in sodium-ion batteries. A micron-sized Co metal-organic framework (MOF) is transformed into a CoS2/N-doped carbon composite, followed by a solvothermal growth of MoS2 nanosheets on the surface. The resulting composite material offers several specific advantages for sodium storage: (i) accelerated sodium-ion diffusion kinetics due to its heterogeneous interface; (ii) shortened ion diffusion path and exposed active sites for sodium storage due to its hierarchical nanosheet architecture; and (iii) homogeneous nitrogen doping of the MOF-derived carbon, which is beneficial for electronic conductivity. Due to these merits, this composite exhibits excellent electrochemical performance with a specific capacity of 596 mAh g-1 after 100 cycles at 0.1 A g-1 and 395 mAh g-1 at 5.0 A g-1.

Broad-Band Photodetectors Based on Copper Indium Diselenide Quantum Dots in a Methylammonium Lead Iodide Perovskite Matrix.

Low-temperature solution-processed methylammonium lead iodide (MAPbI3) crystalline films have shown outstanding performance in optoelectronic devices. However, their high dark current and high noise equivalent power prevent their application in broad-band photodetectors. Here, we applied a facile solution-based antisolvent strategy to fabricate a hybrid structure of CuInSe2 quantum dots (CISe QDs) embedded into a MAPbI3 matrix, which not only enhances the photodetector responsivity, showing a large on/off ratio of 104 at 2 V bias compared with the bare perovskite films, but also significantly (for over 7 days) improves the device stability, with hydrophobic ligands on the CuInSe2 QDs acting as a barrier against the uptake of environmental moisture. MAPbI3/CISe QD-based lateral photodetectors exhibit high responsivities of >0.5 A/W and 10.4 mA/W in the visible and near-infrared regions, respectively, partly because of the formation of a type II interface between the respective semiconductors but most significantly because of the efficient trap-state passivation of the perovskite grain surfaces, and the reduction in the twinning-induced trap density, which stems from both CISe QDs and their organic ligands. A large specific detectivity of 2.2 × 1012 Jones at 525 nm illumination (1 µW/cm2), a fast fall time of 236 µs, and an extremely low noise equivalent power of 45 fW/Hz1/2 have been achieved.

Metal-Organic Framework Derived CoS2 Wrapped with Nitrogen-Doped Carbon for Enhanced Lithium/Sodium Storage Performance.

Transition metal sulfides are attractive electrode materials for both lithium-ion (LIBs) and sodium-ion batteries (SIBs). Starting from micron-sized Co(IPC)·H2O (IPC: 4-(imidazole-1-yl) phthalic acid) and polydopamine as the metal-organic framework (MOF) precursor and carbon source, respectively, we produced a CoS2/C/C composite constituting CoS2 nanoparticles decorated with N-doped carbon layers and subjected to sulfurization. N-doped carbon layers provided a robust network for the CoS2 nanoparticles, enhancing the structural integrity and electronic conductivity of the resulting CoS2/C/C composite, which exhibited electrochemical performance superior to most existing CoS2 composites, and was one of the best among all MOF derived CoS2 anodes for LIBs and SIBs. The use of nanosized CoS2 particles reduced the diffusion length for the transfer of Li+/Na+ ions, resulting in a high specific capacity at a higher current rate. N-doped carbon layers derived from the MOF precursor and polydopamine provided an electrically conductive network between the CoS2 nanoparticles, thus preventing their aggregation and inhibiting adverse side reactions between the electrolyte and the surface of the electrode, and the high pseudocapacitive contribution resulted in the enhanced rate performance of the CoS2/C/C electrodes.

Bottom-up construction of POM-based macrostructures: coordination assembled paddle-wheel macroclusters and their vesicle-like supramolecular aggregation in solution.

A bottom-up approach to obtain nanoclusters and large, uniform vesicle-like structures containing organic functionalized hexamolybdates in solution state were developed. Hexamolybdate functionalized carboxylic acid coordinated with two copper ions to form paddle-wheel tetrapolyoxometalate clusters with the features of macro-ions, which can spontaneously assemble into large, stable blackberry-type structures in suitable solvents, completing a hierarchical organization from small POM molecules to nanoscale complexes and then to supramolecular structures.

Synthesis and assembly of a difunctional core POM cluster with two appended POM cluster caps.

A series of nanorod-like organic-inorganic hybrids based on hexamolybdate and Anderson-type heteropolyoxomolybdates has been prepared using the well-developed DCC protocol. The present work opens a way to flexibly introduce two different functional groups to a hexamolybdate ion and explore thoroughly the whole family of organoimido derivatives for fabricating novel molecular nanostructures with tunable properties.

The chemistry of organoimido derivatives of polyoxometalates.

The chemistry of organoimido derivatives of polyoxometalates (POMs) has received increasing interest. In recent decades, a great development of the synthetic chemistry of organoimido derivatives of POMs using different imido-releasing reagents has taken place, particularly the novel DCC-dehydrating protocol to prepare organoimido derivatives of POMs was developed recently by us and co-workers. Organoimido substituted POMs as valuable building blocks can construct novel nanostructured organic-inorganic hybrid molecular materials in well-developed common organic synthesis methods, such as Pd-catalyzed carbon-carbon coupling and esterification. Therefore, the reactive chemistry of organoimido derivatives of POMs stands for the fascinating future of the chemistry of organoimido derivatives of POMs.

χ-Octamolybdate [Mo(V)4Mo(VI)4O24](4-): an unusual small polyoxometalate in partially reduced form from nonaqueous solvent reduction.

The first mixed-valent octamolybdate anion [Mo(V)(4)Mo(VI)(4)O(24)](4-), termed χ-octamolybdate due to its shape, was obtained by partial reduction of α-(Bu(4)N)(4)-[Mo(8)O(26)] in dry acetonitrile. Single-crystal X-ray structure analysis revealed that the anion includes an unusual Mo(V)(4)O(8) cubane-like cluster core, whose four side faces are capped by four MoO(4) units to form a crosslike cluster. X-ray photoelectron spectroscopy (XPS) and bond valence sum (BVS) calculations were carried out to validate the presence of mixed-valent Mo centers.

Polyoxometalatocyclophanes: controlled assembly of polyoxometalate-based chiral metallamacrocycles from achiral building blocks.

The first polyoxometalatocyclophanes have been synthesized by the covalent linkage of a hexamolybdate cluster and bisarylimido ligands containing flexible chains. These metallamacrocycles are chiral, and some of them can undergo spontaneous resolution. The work provides a new protocol for preparing chiral polyoxometalates (POMs) and chiral metallamacrocycles from achiral building blocks by fastening both ends of a flexible chain onto an achiral POM to remove the symmetric center and mirror.

Rh(II)-catalyzed reaction of alpha-diazocarbonyl compounds bearing beta-trichloroacetylamino substituent: C-H insertion versus 1,2-H shift.

The Rh(II)-carbene reaction is dramatically affected by the neighboring substituents. If the neighboring substituent is an OH group, a1,2-H shift is the exclusive pathway. If it is an OAc group, a 1,2-acetoxy migration is observed. If it is p-toluenesulfonyl group, 1,3 and 1,5-C-H insertion are the major pathways, and the 1,2-H shift is completely suppressed. If the adjacent substituent is a trichloroacetyl amino group, 1,5-C-H insertion competes with the 1,2-hydride shift, and no 1,3-C-H insertion can be observed. Both electronic and steric factors are responsible for the switching of the Rh(II)-carbene reaction pathway. The highly stereoselective 1,5-C-H insertions in Rh(II)-catalyzed reaction of alpha-diazocarbonyl compounds, bearing beta-trichloroacetylamino substituent, can be utilized as a novel way to synthesize five-membered cyclic beta-amino acid derivatives.

Nanoscale chiral rod-like molecular triads assembled from achiral polyoxometalates.

The assembly of two achiral POMs of Lindqvist and Anderson through strong covalent linkages, using bifunctional TRIS with a rotatable C-N single bond, gives two nanoscale rod-like chiral molecular triads with C(2) symmetry, the chirality of which were confirmed by the single crystal X-ray diffraction analyses and solid CD spectroscopy measurements. The enantiopure crystals of these compounds have been obtained by spontaneous resolution upon crystallization in the absence of any chiral source. The present work opens a way to make chiral nanostructures from achiral polyoxoanions, which may have potential applications in asymmetric catalysis, NLO, and ferroelectric materials.

From 0D dimer to 2D network-supramolecular assembly of organic derivatized polyoxometalates with remote hydroxyl via hydrogen bonding.

A series of remote hydroxyl functionalized organoimido derivatives of hexamolybdate, (Bu(4)N)(2)[Mo(6)O(18)(Cres)] (1) (Cres = 4-amino-m-cresol), (Bu(4)N)(2)[Mo(6)O(17)(Cres)(2)] x H(2)O (2), (Bu(4)N)(2)[Mo(6)O(18)(Phen)] x i-PrOH (Phen = p-aminophenol)(3), (Bu(4)N)(2)[Mo(6)O(18)(Phen)] x EtOH (4), (Bu(4)N)(2)[Mo(6)O(17)(Phen)(2)] (5), (Bu(4)N)(2)[Mo(6)O(18)(Naph)] (Naph = 5-amino-1-napheynyl) (6), and (Bu(4)N)(2)[Mo(6)O(18)(Chex)] x 1.5 H(2)O (Chex = trans-4-aminocyclohexanol) (7) were synthesized and characterized by single crystal X-ray diffraction, FT-IR spectra, UV-vis spectra, elemental analysis, (1)H NMR, and cyclic voltammetry. X-ray structural study reveals that intermolecular and intramolecular hydrogen bonding plays an important role in their supramolecular assembly; it is found that (i) bridged oxo ligands of hexamolybdate cluster are more inclined to form hydrogen bonds as acceptors than terminal oxo ligands in this system; (ii) small solvent molecules with hydrogen bonding donor and acceptor, such as water, i-PrOH, and EtOH, usually act as hydrogen bonding bridge in their supramolecular assembly; (iii) hydrogen bonding has an important influence on their anion conformation besides cell packing; (iv) the hydrogen bonding supramolecular assembly of compounds 1-7 demonstrate an interesting change from dimer (3), to 1D infinite single chain (4), to 1D infinite double chain (2), and to 2D network (1, 5, 6, and 7) owing to the alteration of the grafting organic ligand, the substituted number, and the crystallized solvent molecule. To explore their potential application in conductivity, the optical band gap of compounds 1-7 were determined upon their solid state reflectance spectra. Our current study not only surveys systematically hydrogen bonding interaction and supramolecular assembly of remote hydroxyl functionalized organoimido-derivatized hexamolybdates but also provides some available precursors for further modification including esterification.

Iron(III) coordination induced novel 18-metallacrown-6 complex: esterification and isolation of the ligand.

The trianionic heptadentate ligand, (Z)-3-(salicylhydrazinocarbonyl) propenoic acid ((Z)-H(4)shcpa) (1), has been synthesized in good yield and reacted with FeCl(3).6H(2)O, to produce the complex [Fe(III)(6) (C(12)H(9)N(2)O(5))(6)(H(2)O)(2)(CH(3)OH)(4)] x 6CH(3)OH (2). The complex has been characterized by single-crystal X-ray diffraction. In the self-assembly process the ligand was esterified and transferred into (Z)-methyl 3-(salicylhydrazinocarbonyl) propenoate ((Z)-H(3)mshcp) (3). In the structure, the neutral Fe(III) complex contains a 18-membered metallacrown ring consisting of six Fe(III) and six trianionic ligands. The 18-membered metallacrown ring is formed by the succession of six structural moieties of the type [Fe(III)-N-N]. Due to the meridional coordination of the ligands to the Fe(3+) ions, the ligands enforce the stereochemistry of the Fe(3+) ions as a propeller configuration with alternating Lambda/Delta form. The metallacrown can be treated with SnCl(2) to obtain purified ester. In addition, we have also obtained reduced esterified ligand, methyl 3-(salicylhydrazinocarbonyl) propanoate (H3mshcp) (4) with another reductant Zn powder.

1,2-migration in rhodium(II) carbene transfer reaction: remarkable steric effect on migratory aptitude.

A series of diazo carbonyl compounds bearing different substituents have been prepared in order to investigate the steric effect in 1,2-migration reaction of rhodium(II) carbene. Through the investigation on the diazo decomposition of these compounds with Rh2(OAc)4, it was found that the steric effect could dramatically influence the migratory aptitude. In many cases, the steric effect could override the inherent electronic effect of the substituent.