Boosting Electrocatalytic Oxidation of Formic Acid on Ir(IV)-Doped PdAg Alloy Nanodendrites with Sub-5 nm Branches.

The formic acid oxidation reaction (FAOR) represents an important class of small organic molecule oxidation and is central to the practical application of fuel cells. In this study, we report the fabrication of Ir(IV)-doped PdAg alloy nanodendrites with sub-5 nm branches via stepwise synthesis in which the precursors of Pd and Ag were co-reduced, followed by the addition of IrCl3 to conduct an in situ galvanic replacement reaction. When serving as the electrocatalyst for the FAOR in an acidic medium, Ir(IV) doping unambiguously enhanced the activity of PdAg alloy nanodendrites and improved the reaction kinetics and long-term stability. In particular, the carbon-supported PdAgIr nanodendrites exhibited a prominent mass activity with a value of 1.09 A mgPd-1, which is almost 2.0 times and 2.7 times that of their PdAg and Pd counterparts, and far superior to that of commercial Pt/C. As confirmed by the means of the DFT simulations, this improved electrocatalytic performance stems from the reduced overall barrier in the oxidation of formic acid into CO2 during the FAOR and successful d-band tuning, together with the stabilization of Pd atoms. The current study opens a new avenue for engineering Pd-based trimetallic nanocrystals with versatile control over the morphology and composition, shedding light on the design of advanced fuel cell electrocatalysts.

Seeded Growth of Gold-Copper Janus Nanostructures as a Tandem Catalyst for Efficient Electroreduction of CO2 to C2+ Products.

Gold-copper (Au-Cu) Janus nanostructures (Au-Cu Janus NSs) are successfully prepared using N-oleyl-1,3-propanediamine as capping agent and Cu(acac)2 as the precursor in a typical seeded growth strategy. By preferably depositing Cu atoms on one side of concave cubic Au seeds, the Cu part gradually grows larger as more Cu precursors are added, making the size tuning feasible in the range of 74-156 nm. When employed as an electrocatalyst for electrochemical CO2 reduction (CO2 RR), the Au-Cu Janus NSs display superior performance to Au@Cu core-shell NSs and Cu NPs in terms of C2+ products selectivity (67%) and C2+ partial current density (-0.29 A cm-2 ). Combined experimental verification and theoretical simulations reveal that CO spillover from Au sites to the nearby Cu counterparts would enhance CO coverage and thus promote C-C coupling, highlighting the unique structural advantages of the Au-Cu Janus NSs toward deep reduction of CO2 . The current work provides a facile strategy to fabricate tandem catalyst with a Janus structure and validates its structural advantages toward CO2 RR, which are of critical importance for the rational design of efficient CO2 RR catalyst.

Seeded Growth of Au@CuxO Core-Shell Mesoporous Nanospheres and Their Photocatalytic Properties.

We report a facile synthesis of Au@CuxO core-shell mesoporous nanospheres with tunable size in the aqueous phase via seeded growth. The success of the current work relies on the use of a halide-free copper (Cu) precursor and n-oleyl-1,3-propanediamine as a capping agent to facilitate the formation of a copperish oxide shell with a mesoporous structure and the presence of mixed oxidation states of Cu. By varying the amount of spherical Au seeds while keeping other parameters unchanged, their diameters could be readily tuned without noticeable change in morphology. As compared with commercial Cu2O, the as-prepared Au@CuxO core-shell mesoporous nanospheres exhibit the higher adsorption ability, enhanced activity, and excellent stability toward photocatalytic degradation of methyl orange (MO) under visible light irradiation, indicating their potential applications in water treatment.

Crumpled Versus Flat Gold Nanosheets: Temperature-Regulated Synthesis and Their Plasmonic and Catalytic Properties.

We report a high-yield synthesis of gold (Au) nanosheets with tunable size and surface morphology in the aqueous phase. In particular, crumpled and flat Au nanosheets with a thickness of ∼10 nm could be selectively produced in high purity when the reaction was conducted at room temperature and in an ice-water bath, respectively. Unlike Au nanoplates/nanoprisms in the form of well-defined triangles or hexagons documented in previous studies, the current products exhibit random in-plane branches or holes, together with wavy edges. Strong absorbance in the NIR region was observed for all the Au nanosheet products. When serving as electrocatalysts for the ethanol oxidation reaction, the current products exhibited an enhanced activity and operation stability, as compared to quasi-spherical counterparts.

Seed-Morphology-Directed Synthesis of Concave Gold Nanocrystals with Tunable Sizes.

We report the fabrication of concave gold (Au) nanocrystals with a set of morphologies and controlled sizes via seeded growth. Starting with Au seeds with a well-defined morphology and uniform size, cubic and rodlike Au nanocrystals with a noticeable concave feature could be successfully obtained, respectively. We also track the growth process and record the shape evolution process. The effect of several reaction parameters on product morphology, such as capping agent and concentration of Ag+, are systematically investigated. Their optical and electrochemical properties are investigated via UV-vis extinction spectroscopy and cyclic voltammetry, respectively. Compared to spherical counterparts, the current concave Au nanocrystals exhibit a noticeable red shift of the absorbance peak in UV-vis extinction spectra and characterized electrochemical behavior of stepped facets, illustrating the morphological advantage.

Development of a Uricase-Free Colorimetric Biosensor for Uric Acid Based on PPy-Coated Polyoxometalate-Encapsulated Fourfold Helical Metal-Organic Frameworks.

Developing a new cost-effective and reliable approach used for the detection of uric acid (UA) with no requirement of uricase is still very challenging. Herein, an easily realized, cost-effective, and uricase-free approach is reported for selective colorimetric biosensing of UA utilizing polypyrrole (PPy)-coated polyoxometalate-encapsulated fourfold helical metal-organic frameworks Ag5[bimt]2[PMo12O40]·2H2O (Ag5PMo12) as a monolithic peroxidase mimic. It is demonstrated that the as-obtained Ag5PMo12@PPy possesses excellent peroxidase-like activity originated from the synergistic effect to induce catalytic oxidation of colorless 3,3',5,5'-tetramethylbenzidine (TMB) to green oxTMB in the presence of H2O2. Then, the green oxTMB can be selectively converted to colorless TMB induced by UA; thus, UA can inhibit the catalytic oxidation of TMB. Based on these results, a uricase-free colorimetric biosensor for UA is achieved with a linear detection range of 1-50 µM and a detection limit of 0.47 µM. More importantly, the developed biosensor is suited for simple-operated and good reliable UA detection in clinical samples, showing promising application ability in clinical diagnosis and relative fields.

Insights into the lithium diffusion process in a defect-containing porous crystalline POM@MOF anode material.

Rechargeable lithium-ion batteries (LIBs) for potentially low-cost and high-energy-density storage have been intensively researched to meet ever-growing demands. Achieving higher storages and understanding the transporting and storing diffusion process of Li ions are still great challenges. Herein, a porous crystalline polyoxometalate-based metal-organic framework (POM@MOF), H2[Cu(Htrz)5(H2O)2][MoCuO26]0.5·3H2O, with defect sites as a LIB electrode material is reported. The Li-ion diffusion process in the material was investigated using ex situ X-ray photoelectron spectroscopy (XPS) and off-line powder X-ray diffraction (PXRD), indicating that O atoms of POM nano-clusters can be regarded as Li-ion acceptors (storage sites); meanwhile the defect sites (uncoordinated N atoms or -N-H groups) in the crystalline material also participate in the Li-ion storage. The reported porous crystalline POM@MOF material with defects delivers a remarkable Li-ion storage capacity of ca. 700 mA h g-1 in 200 cycles at a current density of 100 mA g-1.

Enhancing the colorimetric detection of H2O2 and ascorbic acid on polypyrrole coated fluconazole-functionalized POMOFs.

A new fluconazole-functionalized polyoxometalate-based metal-organic framework (POMOF) [Ag3(FKZ)2(H2O)2][H3SiW12O40] (AgFKZSiW12) was successfully constructed, and its polypyrrole (PPy) coated composite AgFKZSiW12@PPy was also obtained via a facile 'in situ' oxidation polymerization process. The peroxidase-like activity evaluation indicates that the maximized synergistic effect from the integration of PPy, SiW12 clusters, HFKZ drug molecules, and Ag ions deeply enhanced the overall performance. More importantly, AgFKZSiW12@PPy exhibits the fastest response time (30 s) among all the reported peroxidase mimics to date, including the pristine AgFKZSiW12 (2 min). Moreover, the AgFKZSiW12@PPy-based colorimetric biosensing platform towards H2O2 and ascorbic acid (AA) exhibits limits of detection (LOD) as low as 0.12 µM and 2.7 µM, respectively. This work reveals a promising prospect in medical diagnosis and biotechnology for colorimetric biosensor fabrication with high performance through the introduction of PPy.

Near-infrared quantum cutting platform in thermally stable phosphate phosphors for solar cells.

This study investigated the photoluminescent properties of Tb(3+)-Yb(3+)-, Ce(3+)-Tb(3+)-Yb(3+)-, and Eu(2+)-Yb(3+)-doped KSrPO4. The samples were prepared by a solid-state reaction with various doping concentrations. Emission at near-infrared range was focused on the application of luminescent solar concentrator for solar cells. Quantum cutting (QC) energy transfer was confirmed by the lifetimes of the donor. Near-infrared QC involved emission of Yb(3+) ions was achieved by excitation of Ce(3+), Tb(3+), and Eu(2+) ions, where the energy transfer processes occurred from Ce(3+) to Tb(3+) to Yb(3+), Tb(3+) to Yb(3+), and Eu(2+) to Yb(3+), respectively. In addition, the concentration quenching effect of Yb(3+) ions was avoided by low doping concentrations. The overall quantum efficiencies were calculated, and the maximum efficiency reaches 139%. The energy diagrams for divalent and trivalent rare-earth ions in KSrPO4 host lattice were analyzed. Results of this study demonstrate that heat-stable phosphate phosphors are promising candidates for increasing the efficiency of silicon-based solar cells.

pH- and dopant-dependent CdMoO4:Mn nanocrystals: luminescence and magnetic properties.

CdMoO(4):Mn nanocrystals with a tetragonal crystal structure were prepared by aqueous coprecipitation method at a low temperature of 2 °C under different pH values. The size of the CdMoO(4):Mn nanocrystals of spherical morphology increases with the Mn dopant concentration from 35 to 55 nm for pH = 4. The morphology could be tuned from nanocrystals to microstructures consisting of smaller nanoparticles by the Mn concentration when the pH value of the precursor was increased to 8. The thermal stability of the luminescence and magnetic properties of the Mn-doped samples also depend on the pH and the doping level. The effects of the pH and dopant on the luminescence and magnetic properties, including magnetic susceptibility and electron paramagnetic resonance, were investigated. This approach contributes to better understanding of aqueous chemistry methods to control the growth of nanocrystals.

An intense charge transfer broadband sensitized near-infrared emitting CaLaGa3S3O:Yb3+ phosphor suitable for solar spectral convertor.

A near-infrared (NIR) phosphor, CaLaGa(3)S(6)O:Yb(3+), is developed as a promising solar spectral convertor for Si solar cells. The structure, photoluminescence excitation and emission spectra, concentration effect are investigated. The results show that CaLaGa(3)S(6)O:Yb(3+) has an efficient broad absorption band dominating around the 345 nm ascribing to the charge transfer state (CTS) of Yb(3+)-S(2-) and exhibits an intense NIR emission of Yb(3+) between 920 and 1150 nm, perfectly matching the maximum spectral response of Si solar cells. The NIR emission intensity of CaLaGa(3)S(6)O:Yb(3+) is 12 times as intense as that of a NIR quantum cutting phosphor Ca(2)BO(3)Cl:Ce(3+), Tb(3+), Yb(3+) (CBC) upon 4f-5d excitation of Ce(3+). These results demonstrate that the allowed CTS of Yb(3+)-S(2-) with high absorption cross-section can be an efficient and direct sensitizer harvesting UV-blue photons and greatly enhancing the NIR emission of Yb(3+) ion.

Solvochromic and photodimerization behaviour of 1D coordination polymer via single-crystal-to-single-crystal transformation.

The coordination polymer [Zn(2)(1,2-bda)(2)(bpe)]·MeOH, which exhibits solvochromic effects upon reversible linear alcohol removal and adsorption, can be turned into [Zn(2)(1,2-bda)(2)(tpcb)(0.5)] in two-step SCSC transformations.

Two-color emitting of Ce3+ and Tb3+ co-doped CaLaGa3S6O for UV LEDs.

An intense bluish-green phosphor, CaLaGa(3)S(6)O:Ce(3+),Tb(3+), is developed. The photoluminescence excitation and emission spectra, the lifetime, and the concentration effect are investigated. The results show that an efficient nonradiative energy transfer from Ce(3+) to Tb(3+) occurs and its efficiency is about 11%. Although the efficiency is not high enough, these results demonstrate that a Tb(3+) ion with low 4f-4f absorption efficiency in the near-UV [(n)-UV] region can play the role of activator in a narrow green-emitting phosphor. This is potentially useful in (n)-UV (380-420 nm) GaN-based LEDs through efficient energy feeding by allowing 4f-5d absorption of Ce(3+) with high oscillator strength.