PVP封端剂对Pd纳米晶电催化氧化甲醇和乙醇性能的影响

Direct alcohol fuel cells (DAFCs) have attracted considerable research interest because of their potential application as alternative power sources for automotive systems and portable electronics. Pd-based catalysts represent one of the most popular catalysts for DAFCs due to their excellent electrocatalytic activities in alkaline electrolytes. Thus, it is of great importance to understand the structure-activity relationship of Pd electrocatalysts for alcohol electrocatalysis. Recently, size- and shape- controlled Pd nanocrystals have been successfully synthesized and subsequently used to study the size and shape effects of Pd electrocatalysts on alcohol electrocatalysis, in which the Pd (100) facet exhibited higher electrocatalytic oxidation activity for small alcohol molecules than the Pd (111) and (110) facets. Although it is well known that capping ligands, which are widely used in wet chemistry for the size- and shape-controlled synthesis of metal nanocrystals, likely chemisorb onto the surfaces of the resulting metal nanocrystals and influence their surface structure and surface-mediated properties, such as catalysis, this issue was not considered in previous studies of Pd nanocrystal electrocatalysts for electrocatalytic oxidation of small alcohol molecules. In this study, we prepared polyvinylpyrrolidone (PVP)-capped Pd nanocrystals with different morphologies and sizes and comparatively studied their electrocatalytic activities for methanol and ethanol oxidation in alkaline solutions. The chemisorbed PVP molecules transferred charge to the Pd nanocrystals, and the finer Pd nanocrystals had a higher coverage of chemisorbed PVP, and thus exposed fewer accessible surface sites, experienced more extensive PVP-to-Pd charge transfer, and were more negatively charged. The intrinsic electrocatalytic activity, represented by the electrochemical surface area (ECSA)-normalized electrocatalytic activity, of Pd nanocubes with exposed (100) facets increases with the particle size, indicating that the more negatively-charged Pd surface is less electrocatalytically active. The Pd nanocubes with average sizes between 12 and 19 nm are intrinsically more electrocatalytically active than commercial Pd black electrocatalysts, while the activity of Pd nanocubes with an averages size of 8 nm is less. This suggests that the enhancement effect of the exposed (100) facets surpasses the deteriorative effect of the negatively charged Pd surface for the Pd nanocubes with average sizes between 12 and 19 nm, whereas the deteriorative effect of the negatively charged Pd surface surpasses the enhancement effect of the exposed (100) facets for the Pd nanocubes with average sizes of 8 nm due to the extensive PVP-to-Pd charge transfer. Moreover, the Pd nanocubes with average sizes of 8 nm exhibit similar intrinsic electrocatalytic activity to the Pd nanooctahedra with (111) facets exposed and average sizes of 7 nm, indicating that the electronic structure of Pd electrocatalysts plays a more important role in influencing the electrocatalytic activity than the exposed facet. Since the chemisorbed PVP molecules block the surface sites on Pd nanocrystals that are accessible to the reactants, all Pd nanocrystals exhibit lower mass-normalized electrocatalytic activity than the Pd black electrocatalysts, and the mass-normalized electrocatalytic activity increases with the ECSA. These results clearly demonstrate that the size- and shape-dependent electrocatalytic activity of Pd nanocrystals capped with PVP for methanol and ethanol oxidation should be attributed to both the exposed facets of the Pd nanocrystals and the size-dependent electronic structures of the Pd nanocrystals resulting from the size-dependent PVP coverage and PVP-to-Pd charge transfer. Therefore, capping ligands on capped metal nanocrystals inevitably influence their surface structures and surface-mediated properties, which must be considered for a comprehensive understanding of the structure-activity relationship of capped metal nanocrystals.     

Size-dependent interaction of the poly(N-vinyl-2-pyrrolidone) capping ligand with Pd nanocrystals

Pd nanocrystals were prepared by the reduction of a H(2)PdCl(4) aqueous solution with C(2)H(4) in the presence of different amounts of poly(N-vinyl-2-pyrrolidone) (PVP). Their average size decreases monotonically as the PVP monomer/Pd molar ratio increases up to 1.0 and then does not vary much at higher PVP monomer/Pd molar ratios. Infrared spectroscopy and X-ray photoelectron spectroscopy results reveal the interesting size-dependent interaction of PVP molecules with Pd nanocrystals. For fine Pd nanocrystals capped with a large number of PVP molecules, each PVP molecule chemisorbs with its oxygen atom in the ring; for large Pd nanocrystals capped by a small number of PVP molecules, each PVP molecule chemisorbs with both the oxygen atom and nitrogen atom in the ring, which obviously affects the structure of chemisorbed PVP molecules and even results in the breaking of involved C-N bonds of some chemisorbed PVP molecules. Charge transfer always occurs from a chemisorbed PVP ligand to Pd nanocrystals. These results provide novel insights into the PVP-metal nanocrystal interaction, which are of great importance in the fundamental understanding of surface-mediated properties of PVP-capped metal nanocrystals.     

Replacement of Poly(vinyl pyrrolidone) by Thiols: A Systematic Study of Ag Nanocube Functionalization by Surface-Enhanced Raman Scattering

In this work, we used surface-enhanced Raman scattering (SERS) to monitor the replacement of poly(vinyl pyrrolidone) (PVP) on Ag nanocubes by cysteamine, thiol-terminated PEG, and benzenedithiol. PVP is widely used as a colloidal stabilizer and capping agent to control the shape of Ag (as well as many other noble metals) nanocrystals during synthesis, and to stabilize the final colloidal suspension. However, the surface chemistry of Ag nanocrystals often needs to be tailored for specific applications, so the PVP coating must be removed and/or replaced by other ligands. By monitoring the signature peak from the carbonyl groups of PVP, we show, for the first time, that the PVP adsorbed on the surface of Ag nanocubes was completely replaced by the thiol molecules at room temperature over the course of a few hours. We observed the same trend no matter if the Ag nanocubes were suspended in an aqueous solution of the thiol or supported on a silicon substrate and then immersed in the thiol solution.     

Metal-free inorganic ligands for colloidal nanocrystals: S2-, HS-, Se2-, HSe-, Te2-, HTe-, TeS3(2-), OH-, and NH2- as surface ligands

All-inorganic colloidal nanocrystals were synthesized by replacing organic capping ligands on chemically synthesized nanocrystals with metal-free inorganic ions such as S(2-), HS(-), Se(2-), HSe(-), Te(2-), HTe(-), TeS(3)(2-), OH(-) and NH(2)(-). These simple ligands adhered to the NC surface and provided colloidal stability in polar solvents. The versatility of such ligand exchange has been demonstrated for various semiconductor and metal nanocrystals of different size and shape. We showed that the key aspects of Pearson's hard and soft acids and bases (HSAB) principle, originally developed for metal coordination compounds, can be applied to the bonding of molecular species to the nanocrystal surface. The use of small inorganic ligands instead of traditional ligands with long hydrocarbon tails facilitated the charge transport between individual nanocrystals and opened up interesting opportunities for device integration of colloidal nanostructures.     

Precipitation and recrystallization of uniform CuCl particles formed by aggregation of nanosize precursors

Uniform, spherical CuCl particles were obtained by mixing aqueous solutions of CuCl ₂ and ascorbic acid in the presence of polyvinylpyrrolidone (PVP) as dispersing agent. The size and the uniformity of the resulting particles depended on the volume ratio of the reactant solutions, their concentrations, the distribution of the stabilizers, and the mixing method. The single jet precipitation yielded large spheres of broad size distributions, while the particles obtained by the double jet technique were rather uniform in size. The final colloidal CuCl particles were formed by the aggregation of nanocrystals, initially generated in the system. Depending on the pH of the reaction mixture, these particles slowly change to large CuCl crystals on aging in the mother liquor.     

Self-organized monolayer of nanosized ceria colloids stabilized by poly(vinylpyrrolidone)

Four nanometer colloidal ceria nanocrystals in a fluorite cubic structure have been synthesized via an alcohothermal treatment at 180 degrees C for 24 h from Ce(NO(3))(3)*6H(2)O in ethanol, using various alkylamines including triethylamine, butylamine, and hexadecylamine as the bases and poly(vinylpyrrolidone) (PVP) as the stabilizer. They were characterized by multiple measurements of X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), ultraviolet visible (UV-vis) spectroscopy, dynamic light scattering (DLS), and infrared spectroscopy (IR). The introduction of PVP could effectively stabilize the cerium nuclei against self-aggregation and finally lead to the formation of the CeO(2) colloids. As compared with that of their precipitated counterparts, the UV-vis spectra showed a blue-shifted absorption edge for the as-obtained colloidal nanocrystals, revealing that their surfaces were well-passivated by PVP. Four types of self-organized monolayer patterns (i.e., isolated particles, short chainlike (pseudo-1-D aggregated), pearl necklace-like (1-D aggregated), and dendritic (pseudo-2-D aggregated) alignments) appeared for the as-obtained colloidal particles on the copper TEM grids, due to the delicate balance of the attractive and repulsive forces between the PVP-passivated CeO(2) nanocrystals during the irreversible evaporation of the solvent from various colloidal solutions under ambient conditions. The type of alkylamine and the concentration of PVP were confirmed to be the crucial factors determining the oriented-aggregation dimensionality of the CeO(2) colloids. Possible interparticle interaction modes have been suggested to explain such complex self-organization patterns exhibited by the as-obtained CeO(2) nanocrystals.     

Superdispersible PVP-coated Fe3O4 nanocrystals prepared by a "one-pot" reaction

Poly( N-vinyl-2-pyrrolidone) (PVP)-coated Fe3O4 nanocrystals were prepared by a "one-pot" synthesis through the pyrolysis of ferric triacetylacetonate (Fe(acac)3) in N-vinyl-2-pyrrolidone (NVP). The polymerization of NVP was followed by measuring the shear viscosity of the reaction mixture. The PVP molecules formed in the reaction mixture was investigated by gel permeation chromatography. As the resultant Fe3O4 nanocrystals presented superdispersibility in 10 different types of organic solvents and aqueous solutions with different pH, including 0.01 M phosphate-buffered saline buffer, their hydrodynamic properties in both organic and aqueous systems were investigated by dynamic light-scattering. The results indicated that the PVP-coated Fe3O4 nanocrystals can completely be dispersed forming stable colloidal solutions in both organic solvents and water. Fourier transform infrared spectroscopy results suggested that PVP interacted with Fe3O4 via its carbonyl groups. Further surface analysis by X-ray photoelectron spectroscopy revealed that there were both coordinating and noncoordinating segments of PVP on the particle surface; the molar ratio between them was of 1:2.6.     

纳米Pd的形貌和尺寸可控制备及其1,4-丁炔二醇加氢性能

采用化学还原法合成Pd纳米立方体,并将其作为晶种,进一步合成大尺寸的纳米Pd立方体以及具有不同{100}和{111}晶面比例的纳米Pd多面体.将形貌和尺寸可控的纳米Pd溶胶应用于1,4-丁炔二醇催化加氢的反应中,反应结果表明,纳米Pd的催化性能取决于其尺寸和形貌.{111}晶面的催化活性高于{100}晶面,PVP稳定的Pd胶体对1,4-丁烯二醇均具有较高选择性,具有适当{100}和{111}晶面比例的纳米Pd多面体对1,4-丁烯二醇的选择性可达96%.     

Highly Stable CsPbBr3 Nanocrystal Phosphors by Surface Passivation and Encapsulation

The colloidal all-inorganic CsPbX₃(X=I, Br, Cl) perovskite nanocrystals(NCs) with unique optical properties have attracted considerable attention in the field of semiconductor nanocrystals, but their application is hindered by stability issues caused by surface defects and environmental factors. Usually with inert layer encapsulation, the stability of CsPbX₃ NCs can be significantly enhanced. However, due to the loss of highly dynamic oleic acid/oleylamine ligands, it is usually accompanied by a decrease in the photoluminescence quantum yield(PLQY). Herein, we report a facile method for preparing CsPbBr₃ NCs based green phosphors with high stability and bright emission. With modification of colloidal CsPbBr₃ NCs by di-dodecyldimethylammonium bromide and sequent encapsulation in the as-synthesized mesoporous MOF-5, the green emitting phosphors with enhanced stability and a PLQY of 77% were obtained. The phosphors exhibit enhanced resistance against ambient oxygen, UV light, heat treatment and water. These excellent properties show the potential value of our prepared NCs as stable phosphors in light-emitting devices.     

High-Efficient Ultrathin PdCuMo Porous Nanosheets with Abundant Defects for Oxygen Reduction Reaction

To reduce the over-dependence on Pt, Pd-based catalysts have become one of the most effective candidates for oxygen reduction reaction (ORR). In order to further accelerate the ORR kinetics and strengthen the catalytic performance of Pd catalysts, component optimization and morphology design have been adopted. Although great progress has been made, it is still difficult to obtain porous ultrathin nanosheets with excellent performance by a simple method. Here, ultrathin PdCuMo porous nanosheets (PdCuMo NSs) were successfully prepared. This structure possessed a large specific surface area with rich cavities and structural defects, significantly enhancing its ORR performance. In special, the mass activity of PdCuMo NSs was 1.46 A mg⁻¹ at 0.90 V, which was 12.2, 8.6, and 2.7 times as high as that of Pd/C, Pt/C, and PdCuMo nanoparticles (PdCuMo NPs), respectively. In addition, it had an excellent ability to resist CO poisoning and exhibited remarkable long-term stability.     

Surface chemistry of colloidal PbSe nanocrystals

Solution nuclear magnetic resonance spectroscopy (NMR) is used to identify and quantify the organic capping of colloidal PbSe nanocrystals (Q-PbSe). We find that the capping consists primarily of tightly bound oleic acid ligands. Only a minor part of the ligand shell (0-5% with respect to the number of oleic acid ligands) is composed of tri- n-octylphosphine. As a result, tuning of the Q-PbSe size during synthesis is achieved by varying the oleic acid concentration. By combining the NMR results with inductively coupled plasma mass spectrometry, a complete Q-PbSe structural model of semiconductor core and organic ligands is constructed. The nanocrystals are nonstoichiometric, with a surface that is composed of lead atoms. The absence of surface selenium atoms is in accordance with an oleic acid ligand shell. NMR results on a Q-PbSe suspension, stored under ambient conditions, suggest that oxidation leads to the loss of oleic acid ligands and surface Pb atoms, forming dissolved lead oleate.     

Laser-induced silver nanocrystal formation in polyvinylpyrrolidone solutions

We report unusual laser-induced shape conversions of silver nanoparticles dispersed in polyvinylpyrrolidone (PVP) aqueous solutions. Silver nanocrystals such as nanoplates and nanorods were formed using laser irradiation for colloidal silver nanoparticles prepared using laser ablation in aqueous solutions of PVP. Differing from the nanocrystal formation observed in neat water and halide solutions, which were induced by weak laser or fluorescent-light irradiation, the nanocrystal formation in PVP solutions was induced by strong laser irradiation. On the other hand, nanocrystal formation was not observed in polyvinylalcohol (PVA) solutions, in which fusion of nanoparticles were prominent. It is proposed that the nanocrystals were formed from fragmented nanoparticles protected by PVP via a ripening process.     

Ru修饰Pd二十四面体纳米晶的合成及其甲醇电催化氧化性能

表面结构控制和表面异种金属修饰是调控催化剂反应性的重要方法。因此,我们结合高指数晶面结构的高反应性与表面修饰异种金属,合成具有{730}高指数晶面的钯二十四面体纳米晶,并通过循环伏安扫描电沉积法得到Ru修饰的钯二十四面体纳米晶。电化学测试结果表明,低的Ru覆盖度(θ_(Ru)=0.08)可显著提高对碱性介质中甲醇电氧化的催化性能。电化学原位红外光谱结果表明,少量Ru的修饰没有减少CO的生成,而是促进了低电位下甲醇氧化成甲酸根。     

Morphology and surface States of colloidal probucol nanoparticles evaluated by atomic force microscopy

Morphology and surface states of colloidal probucol nanoparticles after dispersion of probucol/polyvinylpyrrolidone (PVP)/sodium dodecyl sulphate (SDS) ternary ground mixture into water were investigated by atomic force microscopy (AFM). The observed particles had core-shell structure, i.e. drug nanocrystals were covered with PVP and SDS complex. The AFM phase image and the force curve analyses indicated that probucol nanoparticles with PVP K17 showed layer structure, compared to those with PVPK12. The structural difference was explainable in terms of the molecular states of PVP-SDS complex on the particle surface. These findings support not only the mechanism of drug nanoparticle formation but also the in vivo absorption results with the almost same particle size of ca. 40 nm.     

A general route to synthesize water-dispersive noble metal-iron oxide bifunctional hybrid nanoparticles

This communication describes a simple, general route for preparing bifunctional hybrid nanoparticles based on direct adsorption and spontaneous reduction of Ag(+) and Pd(2+) onto the surface of carbon-encapsulated superparamagnetic colloidal nanoclusters. Because of the existence of carbon coating and surface hydrophilic carboxyl, the bifunctional hybrid nanoparticles show excellent water-dispersity. In addition, the size (35 nm-86 nm) and number of Ag nanocrystals can be tuned by changing the molar ratios and reaction concentration between Ag(+) and nanoclusters.     

Controlling nanocrystal superlattice symmetry and shape-anisotropic interactions through variable ligand surface coverage

The assembly of colloidal nanocrystals (NCs) into superstructures with long-range translational and orientational order is sensitive to the molecular interactions between ligands bound to the NC surface. We illustrate how ligand coverage on colloidal PbS NCs can be exploited as a tunable parameter to direct the self-assembly of superlattices with predefined symmetry. We show that PbS NCs with dense ligand coverage assemble into face-centered cubic (fcc) superlattices whereas NCs with sparse ligand coverage assemble into body-centered cubic (bcc) superlattices which also exhibit orientational ordering of NCs in their lattice sites. Surface chemistry characterization combined with density functional theory calculations suggest that the loss of ligands occurs preferentially on {100} than on reconstructed {111} NC facets. The resulting anisotropic ligand distribution amplifies the role of NC shape in the assembly and leads to the formation of superlattices with translational and orientational order.     

A novel strategy for boosting the photoluminescence quantum efficiency of CdSe nanocrystals at room temperature

Highly luminescent colloidal nanocrystals have wide applications in bioimaging and various optoelectronic devices.Herein we report a facile and mild procedure by combining S2-treatment and binary ligand passivation,which can efficiently enhance the luminescent property of CdSe nanocrystals at room temperature.The photoluminescence quantum yield of as-treated CdSe nanocrystals exhibits drastic enhancement(e.g.,188 times for CdSe nanorods)after this dual-passivation treatment.The methodology proposed here can be applied to various CdSe nanocrystals,regardless of their sizes,shapes,and crystal structures.     

胶体铜催化丙烯腈水合的高选择性及其活性中心结构的研究

研究了胶体铜催化丙烯腈水合制丙烯酰胺的高选择性与活性中心结构的关系. 在聚乙烯吡咯烷酮(PVP)保护下, 用肼和氢氧化钠混合液还原CuCl2制得胶体铜, 用其催化丙烯腈水合反应, 选择性达到100％, 产生高选择性的原因如下: (1) 胶体铜的活性中心不是胶粒表面的点缺陷, 而是胶体铜颗粒表面的位错端点. (2) 由于胶体铜具有高硬度和高强度的力学特性, 保证了活性中心结构的稳定性; 胶体铜颗粒的平均粒径(45 nm)超过晶粒的特征长度, 进一步保证了活性中心的稳定性.     

Carbon monoxide-assisted synthesis of single-crystalline Pd tetrapod nanocrystals through hydride formation

Carbon monoxide can adsorb specifically on Pd(111) to induce the formation of unique Pd nanostructures. In the copresence of CO and H(2), single-crystalline Pd tetrapod nanocrystals have now been successfully prepared. The Pd tetrapods are enclosed by (111) surfaces and are yielded through hydride formation. Density functional theory calculations revealed that the formation of PdH(x) in the presence of H(2) reduces the binding energy of CO on Pd and thus helps to decrease the CO coverage during the synthesis, which is essential to the formation of the PdH(x) tetrapod nanocrystals. In addition to tetrapod nanocrystals, tetrahedral nanocrystals were also produced in the copresence of CO and H(2) when the reaction temperature was ramped to further lower the CO coverage. Upon aging in air, the as-prepared PdH(x) nanocrystals exhibited a shape-dependent hydrogen releasing behavior. The conversion rate of PdH(x) tetrapod nanocrystals into metallic Pd was faster than that of tetrahedral nanocrystals.     

Nanocrystal ligand exchange with 1,2,3,4-thiatriazole-5-thiolate and its facile in situ conversion to thiocyanate

The 1,2,3,4-thiatriazole-5-thiolate anion (TTT(-)) was found to be a strongly binding ligand for CdSe nanocrystals, quantitatively exchanging various long-chain ligands to yield stable colloidal suspensions in common polar solvents. The TTT(-) ligand thermolyzes at <100 °C to produce thiocyanate in situ, resulting in reduced quantum confinement in nanocrystal films. CdSe(TTT) possesses far higher colloidal stability than CdSe(SCN), and that, together with the facile synthesis of TTT(-), implies that this is a useful ligand for nanocrystal applications as a masked thiocyanate.