Self-Assembly of Polyoxometalate-Based Sub-1†nm Polyhedral Building Blocks into Rhombic Dodecahedral Superstructures.

Self-assembly of subnanometer (sub-1 nm) scale polyhedral building blocks can yield some superstructures with novel and interesting morphology as well as potential functionalities. However, achieving the self-assembly of sub-1 nm polyhedral building blocks is still a great challenge. Herein, through encapsulating the titanium-substituted polyoxometalate (POM, K7 PTi2 W10 O40 ) with tetrabutylammonium cations (TBA+ ), we first synthesized a sub-1 nm rhombic dodecahedral building block by further tailoring the spatial distribution of TBA+ on the POM. Molecular dynamics (MD) simulations demonstrated the eight TBA+ cations interacted with the POM cluster and formed the sub-1 nm rhombic dodecahedron. As a result of anisotropy, the sub-1 nm building blocks have self-assembled into rhombic dodecahedral POM (RD-POM) assemblies at the microscale. Benefiting from the regular structure, Br- ions, and abundant active sites, the obtained RD-POM assemblies exhibit excellent catalytic performance in the cycloaddition of CO2 with epoxides without co-catalysts. This work provides a promising approach to tailor the symmetry and structure of sub-1 nm building blocks by tuning the spatial distribution of ligands, which may shed light on the fabrication of superstructures with novel properties by self-assembly.

Dominant Role of Hole Transport Pathway in Achieving Record High Photoconductivity in Two-Dimensional Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) with mobile charges have attracted significant attention due to their potential applications in photoelectric devices, chemical resistance sensors, and catalysis. However, fundamental understanding of the charge transport pathway within the framework and the key properties that determine the performance of conductive MOFs in photoelectric devices remain underexplored. Herein, we report the mechanisms of photoinduced charge transport and electron dynamics in the conductive 2D M-HHTP (M=Cu, Zn or Cu/Zn mixed; HHTP=2,3,6,7,10,11-hexahydroxytriphenylene) MOFs and their correlation with photoconductivity using the combination of time-resolved terahertz spectroscopy, optical transient absorption spectroscopy, X-ray transient absorption spectroscopy, and density functional theory (DFT) calculations. We identify the through-space hole transport mechanism through the interlayer sheet π-π interaction, where photoinduced hole state resides in HHTP ligand and electronic state is localized at the metal center. Moreover, the photoconductivity of the Cu-HHTP MOF is found to be 65.5 S m-1 , which represents the record high photoconductivity for porous MOF materials based on catecholate ligands.

The effect of interlayer water of metal-modified montmorillonite for catalytic ozonation.

The catalytic ozonation-based advanced oxidation process (AOP) is applied to remove nondegradable chemical oxygen demand (COD), while the application in industry is limited by the economics and activity of catalysts. In this study, we demonstrate that by taking atrazine (ATZ) as a model pollutant, the removal rates of catalytic ozonation were negatively correlated with the interlayer water content of metal-modified montmorillonite (Mx@MMT), instead of the loadings metals. Among the modified MMT, Zn0.1@MMT achieved 83.2% degradation of ATZ within 15 min, and corresponding removal rates of COD and total organic carbon (TOC) reached 40.3% and 46.5%, respectively. Detailed EPR and quenching experiments identified that hydroxyl radicals (HO•) were the main reactive oxygen species and QTOF/MS/MS analysis helped to propose a possible degradation pathway of ATZ. Moreover, the catalytic performance of Zn0.1@MMT under different conditions was also systematically evaluated.

Tafel Analysis Guided Optimization of ZnNP-O-C Catalysts for the Selective 2-Electron Oxygen Reduction Reaction in Neutral Media.

The lack of characterizations of the adsorption capability toward intermediates during reactions causes difficulties in determining the structural optimization principle of the catalysts for the 2-electron oxygen reduction reaction (2e- ORR). Here, a Tafel-θ method is proposed to evaluate the surface coverage (θ) of important intermediates (*OOH and *OH) on the material surface and further help optimize the catalyst. With the assistance of Tafel-θ analysis, a Zn nanoparticle incorporated oxygen-doped carbon (ZnNP-O-C) catalyst with high 2e- ORR performance (onset of ∼0.57 V and selectivity of >90.4%) in neutral media was achieved. Both the theoretical calculation and characterization results are consistent with the Tafel-θ deduction, revealing that an appropriate ratio of Zn nanoparticles and bridging O can optimize the *OOH adsorption/desorption strength of the adjacent carbon site. This study not only provides an advanced ZnNP-O-C catalyst for electrochemical H2O2 production but also proposes a fast and precise method for the comprehensive assessment of future catalysts.

Single molecule-mediated assembly of polyoxometalate single-cluster rings and their three-dimensional superstructures.

The assembly of atomically precise clusters into superstructures has tremendous potential in structural tunability and applications. Here, we report a series of single-cluster nanowires, single-cluster nanorings, and three-dimensional superstructure assemblies built by POM clusters. By stepwise tuning of interactions at molecular levels, the configurations can be varied from single-cluster nanowires to nanorings. A series of single-cluster nanostructures in different configurations can be achieved with up to 15 kinds of POM clusters. The single-cluster nanowires and three-dimensional superstructures perform enhanced activity in the catalytic and electrochemical sensing fields, illustrating the universal functionality of single-cluster assemblies.

2D Covalent Organic Frameworks as Intrinsic Photocatalysts for Visible Light-Driven CO2 Reduction.

Covalent organic framework (COF) represents an emerging class of porous materials that have exhibited great potential in various applications, particularly in catalysis. In this work, we report a newly designed 2D COF with incorporated Re complex, which exhibits intrinsic light absorption and charge separation (CS) properties. We show that this hybrid catalyst can efficiently reduce CO2 to form CO under visible light illumination with high electivity (98%) and better activity than its homogeneous Re counterpart. More importantly, using advanced transient optical and X-ray absorption spectroscopy and in situ diffuse reflectance spectroscopy, we unraveled three key intermediates that are responsible for CS, the induction period, and rate limiting step in catalysis. This work not only demonstrates the potential of COFs as next generation photocatalysts for solar fuel conversion but also provide unprecedented insight into the mechanistic origins for light-driven CO2 reduction.

Hierarchical Nanotubes Constructed by Carbon-Coated Ultrathin SnS Nanosheets for Fast Capacitive Sodium Storage.

Tin(II) sulfide (SnS) has been an attractive anode material for sodium ion batteries. Herein, an elegant templating method has been developed for the rational design and synthesis of hierarchical SnS nanotubes composed of ultrathin nanosheets. In order to enhance the electrochemical performance, carbon coated hierarchical SnS nanotubes (denoted as SnS@C nanotubes) have also been obtained by simply adding glucose into the reaction system. Benefiting from their unique structural merits, the SnS@C nanotubes exhibit enhanced sodium storage properties in terms of good cycling performance and superior rate capability.

Carbon-Incorporated Nickel-Cobalt Mixed Metal Phosphide Nanoboxes with Enhanced Electrocatalytic Activity for Oxygen Evolution.

Hollow nanostructures have attracted increasing research interest in electrochemical energy storage and conversion owing to their unique structural features. However, the synthesis of hollow nanostructured metal phosphides, especially nonspherical hollow nanostructures, is rarely reported. Herein, we develop a metal-organic framework (MOF)-based strategy to synthesize carbon incorporated Ni-Co mixed metal phosphide nanoboxes (denoted as NiCoP/C). The oxygen evolution reaction (OER) is selected as a demonstration to investigate the electrochemical performance of the NiCoP/C nanoboxes. For comparison, Ni-Co layered double hydroxide (Ni-Co LDH) and Ni-Co mixed metal phosphide (denoted as NiCoP) nanoboxes have also been synthesized. Benefiting from their structural and compositional merits, the as-synthesized NiCoP/C nanoboxes exhibit excellent electrocatalytic activity and long-term stability for OER.

A facile and general strategy for the synthesis of porous flowerlike Pt-based nanocrystals as effective electrocatalysts for alcohol oxidation.

In this paper, porous flowerlike Pt-based (Pt, PdPt, RhPt and RhPdPt) nanocrystals were successfully achieved by a simple, economic, environmentally friendly route under the same synthetic conditions at 85 °C. The electrocatalytic properties of these flowerlike Pt-based nanocrystals toward alcohols (glycol, glycerol, methanol and ethanol) oxidation were investigated and they displayed enhanced catalytic performance compared with commercial Pt black. Among them, porous Pd45.5Pt54.5 nanoflowers showed the best catalytic performance with significant mass activity and long-term stability. More importantly, the current synthesis strategy can be easily amplified to gram-scale production.

Sub-1 nm Nickel Molybdate Nanowires as Building Blocks of Flexible Paper and Electrochemical Catalyst for Water Oxidation.

Sub-1 nm, extremely long nickel molybdate nanowires are synthesized based on a good/poor solvent system. The ultrathin nanowires can be hierarchically assembled into flexible, free-standing films with good mechanical properties. Compared with the large-size counterpart, nickel molybdate ultrathin nanowires display promising oxygen evolution reaction catalytic performance derived from the ultrathin feature.

Surfactant encapsulated palladium-polyoxometalates: controlled assembly and their application as single-atom catalysts.

The challenge with single-atom catalysts (SACs) is in designing a highly definite structure with accurate location of the single atom and high catalytic efficiency. The noble metal substituted polyoxometalates seem to be a kind of SAC because of their well resolved crystal structure. Here, we got two kinds of assembly structures (nanorolls and hollow spindles) based on the palladium substituted Wells-Dawson polyoxometalate (Pd-POM), which consists of isolated Pd atoms. Both the nanorolls and hollow spindles showed high catalytic activity for both the Suzuki-Miyaura coupling reaction and semihydrogenation reaction. The difference of the chemical surroundings between the nanorolls and hollow spindles leads to their discrepancy in the catalytic activity of semihydrogenation.

Zinc Sulfide Nanosheet-Based Hybrid Superlattices with Tunable Architectures Showing Enhanced Photoelectrochemical Properties.

Zinc sulfide nanosheet-based hybrid superlattices with tunable periodicities and rod-like or tubular morphologies are constructed by the spontaneous assembly of nanosheets as they grow in amine solution. The as-prepared architectures can be used as an enhanced electrode for photocurrent response and converted to other functional materials.

Size-controllable synthesis of trimetallic RhPdPt island-shaped nanoalloys with enhanced electrocatalytic performance for ethanol oxidation in alkaline medium.

Size-controllable, high-yield, island-shaped RhPdPt trimetallic nanocrystals with sub-2.0 nm islands have been successfully synthesized through a facile aqueous solution approach. The results of X-ray diffraction (XRD), energy-dispersive X-ray (EDX) line scanning and elemental mapping analysis showed the as-synthesized RhPdPt nanocrystals are alloy structures. These island-shaped RhPdPt trimetallic nanoalloys showed a composition-dependent electrocatalytic performance for ethanol oxidation in alkaline medium. Due to the special structure and intermetallic synergies, the Rh10Pd40Pt50 nanoalloys exhibited an enhanced catalytic activity and durability relative to island-shaped Pd50Pt50 bimetallic nanoalloys and commercial Pt black. The peak current density for Rh10Pd40Pt50 nanoalloys was 1.81 and 1.38 times that for commercial Pt black and Pd50Pt50 nanoalloys, respectively. In addition, the peak potential on Rh10Pd40Pt50 nanoalloys decreased 42 mV relative to commercial Pt black and Pd50Pt50 nanoalloys.

Nanocrystals of Uranium Oxide: Controlled Synthesis and Enhanced Electrochemical Performance of Hydrogen Evolution by Ce Doping.

A preliminary study of the growth of 0D, 1D, and 2D nanostructures of uranium oxides with feature sizes from several nanometers down to 1 nm are presented. Cerium is successfully doped into these oxides and its influence on the growth dynamics and electrochemical performance investigated.

A 1D/2D helical CdS/ZnIn2 S4 nano-heterostructure.

Multidimensional nano-heterostructures (NHSs) that have unique dimensionality-dependent integrative and synergic effects are intriguing but still underdeveloped. Here, we report the first helical 1D/2D epitaxial NHS between CdS and ZnIn2S4. Experimental and theoretical studies reveal that the mismatches in lattice and dangling bonds between 1D and 2D units govern the growth procedure. The resulting well-defined interface induces the delocalized interface states, thus facilitate the charge transfer and enhance the performance in the photoelectrochemical cells. We foresee that the mechanistic insights gained and the electronic structures revealed would inspire the design of more complex 1D/2D NHSs with outstanding functionalities.

Ultrathin Pt-Cu nanosheets and nanocones.

In this work, we have successfully synthesized free-standing ultrathin Pt-Cu alloy nanosheets of 4-6 atom thickness with tunable lateral size from 10 to 50 nm. The nanosheets with diameters >20 nm can be converted into nanocones in a controllable way. These nanosheets and nanocones exhibit excellent electrocatalytic activities for the oxidation of ethanol in comparison to commercial Pt black and Pt/C catalysts.

Polyoxometalate-based supramolecular gel.

Self-assemblyings of surfactant-encapsulated Wells-Dawson polyoxometalates (SEPs) nanobuilding blocks in butanone and esters yielded supramolecular gels showing thermo and photo responsive properties. The gels can be further polymerized if unsaturated esters were used and subsequently electrospinned into nanowires and non-woven mats. The as-prepared non-woven mats have a Young's modulus as high as 542.55 MPa. It is believed that this supramolecular gel is a good platform for polyoxometalates processing.

Understanding the "tailoring synthesis" of CdS nanorods by O2.

Parameters such as solution concentrations and composition of the ambient atmosphere are known to be important in phase and morphology control in the solvothermal synthesis of CdS semiconductor nanorods (NRs), but a clear understanding of the underlying mechanisms involved is lacking. In this work, a series of experiments were performed to demonstrate that the key factor affecting the phase and morphology of CdS NRs is the amount of O(2) in the space above the reaction solution in the sealed vessel relative to the amount of precursors in solution: O(2)-depleted conditions resulted in more cubic phase CdS and thick polycrystalline NRs with an aspect ratio usually less than 3, which have small blue shifts in band-edge emission and little surface trap emission, while O(2)-rich conditions resulted in more hexagonal-phase CdS and slim single-crystal NRs, which have significantly blue shifted band-edge emission and relatively strong surface trap emission. Thus, increasing the amount of solution in the vessel, changing the ambient atmosphere from air to N(2), and increasing the reagent concentration all lower the molar ratio of O(2) to reagents and lead to more cubic phase and thicker NRs. The results indicate that the composition of the "empty" section of the reaction vessel plays as important a role as the composition of the liquid in determining the phase and morphology, something that has been overlooked in earlier work. A mechanism to explain the effect of oxygen on the nucleation and growth stages has been proposed on the basis of those results and further supported by shaking experiments and ZnS NR synthesis manipulation. The CdS NRs synthesized under different conditions showed obvious differences in photocatalytic activity, which indicated that controlling the synthetic process can lead to materials with tailored photocatalytic activity.