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1.
A facile strategy was reported to fabricate a novel Pt‐based metal oxide double‐shelled hollow nanospheres (MDSHs), which avoided the traditional tedious procedures. It was attractive that the formation mechanism of DSHs involved redeposition of etch‐released silica species and self‐assembly of metal oxide units. To verify the successful synthesis and structure features of Pt‐LCDSHs catalyst, the as‐prepared samples were characterized by several techniques, such as SEM, N2 adsorption–desorption isotherm analysis, TEM, EDX, XRD and XPS. Results indicated that all of MDSHs possessed double‐shelled structures with both the inner and outer shells composing of metal oxide units. Interestingly, the metal oxide of the DHSs could offer abundant active points for Pt NPs and the space between the double shells also could be filled with Pt NPs. What's more, compared with the pure samples, the Pt‐embedded La2O3‐CeO2‐DSHs exhibited the highest catalytic performance (6.58 × 10?3 min?1) and good reusability with a conversion of 94% even after eight cycles, which were evaluated by means of the reduction of 4‐nitrophenol monitored by UV–vis spectra. Finally, a possible reaction mechanism for the reduction reaction on Pt‐based La2O3‐CeO2‐DSHs was also proposed.  相似文献   

2.
《化学:亚洲杂志》2018,13(18):2714-2722
Currently, the base‐free aerobic oxidation of biomass‐derived 5‐hydroxymethylfurfural (HMF) to produce 2,5‐furandicarboxylic acid (FDCA) is attracting intense interest due to its prospects for the green, sustainable, and promising production of biomass‐based aromatic polymers. Herein, we have developed a new Pt catalyst supported on nitrogen‐doped‐carbon‐decorated CeO2 (NC‐CeO2) for the aerobic oxidation of HMF in water without the addition of any homogeneous base. It was demonstrated that the small‐sized Pt particles could be well dispersed on the surface of the hybrid NC‐CeO2 support, and the activity of the supported Pt catalyst depended strongly on the surface structure and properties of the catalysts. The as‐fabricated Pt/NC‐CeO2 catalyst, with abundant surface defects, enhanced basicity, and favorable electron‐deficient metallic Pt species, enabled an almost 100 % yield of FDCA in water with molecular oxygen (0.4 MPa) at 110 °C for 8 h without the addition of any homogeneous base, which is indicative of exceptional catalytic performance. Furthermore, this Pt/NC‐CeO2 catalyst also showed good stability and reusability owing to strong metal–support interactions. An understanding of the role of surface structural defects and basicity of the hybrid NC‐CeO2 support provides a basis for the rational design of high‐performance and stable supported metal catalysts with practical applications in various transformations of biomass‐derived compounds.  相似文献   

3.
A Cu–Pt nanoparticle catalyst supported on TiO2 nanowires (NWs) was prepared through regenerative counterion exchange–reduction using polyelectrolyte brush as template. Cationic polydimethyl aminoethyl methacrylate brushes were grafted onto TiO2 NWs. Cu–Pt nanocrystals were produced by anionic counterions CuCl42? and PtCl62? bound with the polymer brush through in situ reduction with NaBH4 of high density and low polydispersity. The as‐prepared TiO2 NWs/polymer brush/Cu–Pt was characterized by Fourier transform infrared spectroscopy (FT‐IR spectrometry), X‐ray photoelectron spectroscopy, transmission electron microscopy, and UV–Vis adsorption spectrometry analyses. Results showed that the highly dispersed Cu and Pt nanoparticles were present on the surface of the TiO2 NWs/polymer brush. The resultant TiO2 NWs/polymer brush/Cu–Pt exhibited extremely high catalytic activity and reduced p‐nitrophenol at room temperature. Copyright © 2017 John Wiley & Sons, Ltd.  相似文献   

4.
The effect of the microstructure of titanium dioxide on the structure, thermal stability, and catalytic properties of supported CuO/TiO2 and CuO/(CeO2-TiO2) catalysts in CO oxidation was studied. The formation of a nanocrystalline structure was found in the CuO/TiO2 catalysts calcined at 500°C. This nanocrystalline structure consisted of aggregated fine anatase particles about 10 nm in size and interblock boundaries between them, in which Cu2+ ions were stabilized. Heat treatment of this catalyst at 700°C led to a change in its microstructure with the formation of fine CuO particles 2.5–3 nm in size, which were strongly bound to the surface of TiO2 (anatase) with a regular well-ordered crystal structure. In the CuO/(CeO2-TiO2) catalysts, the nanocrystalline structure of anatase was thermally more stable than in the CuO/TiO2 catalyst, and it persisted up to 700°C. The study of the catalytic properties of the resulting catalysts showed that the CuO/(CeO2-TiO2) catalysts with the nanocrystalline structure of anatase were characterized by the high-est activity in CO oxidation to CO2.  相似文献   

5.
利用沉积沉淀法制备了Pt/TiO2催化剂, 将其在不同温度下焙烧, 以得到不同颗粒尺寸的Pt. 并将这些样品用于CO催化氧化反应以及反应动力学研究. 结果表明: 焙烧温度对催化剂有明显影响, Pt 颗粒尺寸随着焙烧温度的升高而增加; 与此同时, CO催化活性随焙烧温度的升高呈先增加后降低的趋势, 其中, 400℃焙烧的样品表现出最高的催化活性. 反应动力学结果表明, 催化剂上CO氧化反应表观速率方程为r=5.4×10-7pCO0.17pO20.36,说明在该催化剂上CO氧化遵循Langmuir-Hinshelwood机理. 同时, 对催化剂进行了CO化学吸附红外光谱和O2化学吸附表征. 结果表明, 随着焙烧温度的升高, 催化剂上CO和O2吸附量均呈现先升高后降低的趋势, 这与反应结果和反应动力学方程一致, 说明反应受到催化剂表面上CO和O2吸附浓度的影响. 而在400℃焙烧的催化剂上, CO和O2吸附量均最高, 因此其反应活性也最好. 这可能是焙烧过程影响了Pt 和TiO2之间的相互作用引起的.  相似文献   

6.
Recently, the emergence of photoactive metal–organic frameworks (MOFs) has given great prospects for their applications as photocatalytic materials in visible‐light‐driven hydrogen evolution. Herein, a highly photoactive visible‐light‐driven material for H2 evolution was prepared by introducing methylthio terephthalate into a MOF lattice via solvent‐assisted ligand‐exchange method. Accordingly, a first methylthio‐functionalized porous MOF decorated with Pt co‐catalyst for efficient photocatalytic H2 evolution was achieved, which exhibited a high quantum yield (8.90 %) at 420 nm by use sacrificial triethanolamine. This hybrid material exhibited perfect H2 production rate as high as 3814.0 μmol g?1 h?1, which even is one order of magnitude higher than that of the state‐of‐the‐art Pt/MOF photocatalyst derived from aminoterephthalate.  相似文献   

7.
Highly dispersed Pt‐CeO2 hybrids arched on reduced graphene oxide (Pt‐CeO2/rGO) were facilely synthesized by a combination of the reverse micelle technique and a redox reaction without any additional reductant or surfactant. Under a N2 atmosphere, the redox reaction between Ce3+ and Pt2+ occurs automatically in alkaline solution, which results in the formation of Pt‐CeO2/rGO nanocomposites (NCs). The as‐synthesized Pt‐CeO2/rGO NCs exhibit superior catalytic performance relative to that shown by the free Pt nanoparticles, Pt/rGO, Pt‐CeO2 hybrid, and the physical mixture of Pt‐CeO2 and rGO; furthermore, the nanocomposites show significantly better activity than the commercial Pt/C catalyst toward the hydrolysis of ammonia borane (NH3BH3) at room temperature. Moreover, the Pt‐CeO2/rGO NCs have remarkable stability, and 92 % of their initial catalytic activity is preserved even after 10 runs. The excellent activity of the Pt‐CeO2/rGO NCs can be attributed not only to the synergistic structure but also to the electronic effects of the Pt‐CeO2/rGO NCs among Pt, CeO2, and rGO.  相似文献   

8.
The hydrogenation of crotonaldehyde in the presence of supported platinum nanoparticles was used to determine how the interaction between the metal particles and their support can control catalytic performance. Using gas‐phase catalytic reaction studies and in situ sum‐frequency generation vibrational spectroscopy (SFG) to study Pt/TiO2 and Pt/SiO2 catalysts, a unique reaction pathway was identified for Pt/TiO2, which selectively produces alcohol products. The catalytic and spectroscopic data obtained for the Pt/SiO2 catalyst shows that SiO2 has no active role in this reaction. SFG spectra obtained for the Pt/TiO2 catalyst indicate the presence of a crotyl‐oxy surface intermediate. By adsorption through the aldehyde oxygen atom to an O‐vacancy site on the TiO2 surface, the C?O bond of crotonaldehyde is activated, by charge transfer, for hydrogenation. This intermediate reacts with spillover H provided by the Pt to produce crotyl alcohol.  相似文献   

9.
Metal–support interactions (MSIs) and particle size play important roles in catalytic reactions. For the first time, silver nanoparticles supported on CeO2‐SBA‐15 supports are reported that possess tunable particle size and MSIs, as prepared by microwave (MW) irradiation, owing to strong charge polarization of CeO2 clusters (i.e., MW absorption). Characterizations, including TEM, X‐ray photoelectron spectroscopy, and extended X‐ray absorption fine structure, were carried out to disclose the influence of CeO2 contents on the Ag particle size, MSI effect between Ag nanoparticles and CeO2‐SBA‐15 supports, and the strong MW absorption of CeO2 clusters that contribute to the MSIs during Ag deposition. The Ag particle sizes were controllably tuned from 1.9 to 3.9 nm by changing the loading amounts of CeO2 from 0.5 to 2.0 wt %. The Ag nanoparticle size was predominantly responsible for the high turnover frequency (TOF) of 0.41 min?1 in ammonia borane dehydrogenation, whereas both particle size and MSIs contributed to the high TOF of 555 min?1 in 4‐nitrophenol reduction for Ag/0.5CeO2‐SBA‐15, which were twice as large as those of Ag/SBA‐15 without CeO2 and Ag/CeO2‐SBA‐15 prepared by conventional oil‐bath heating.  相似文献   

10.
Pt‐Co/Al2O2 catalyst has been studied for CO2 reforming of CH4 to synthesis gas. It was found that the catalytic performance of me catalyst was sensitive to calcination temperature. When Co/Al2O3 was calcined at 1473 K prior to adding a small amount of Pt to it, the resulting bimetallic catalyst showed high activity, optimal stability and excellent resistance to carbon deposition, which was more effective to the reaction than Co/Al2O3 and Pt/Al2O3 catalysts. At lower metal loading, catalyst activity decreased in the following order: Pt‐Co/ Al2O3 > Pt/Al2O3 > Co/Al2O3. With 9% Co, the Co/Al2O3 calcined at 923 K was also active for CO2 reforming of CH4, however, its carbon formation was much more fast man that of the Pt‐Co/Al2O3 catalyst. The XRD results indicated that Pt species well dispersed over the bimetallic catalyst. Its high dispersion was related to the presence of CoAl2O4, formed during calcining of Co/Al2O3 at high temperature before Pt addition. Promoted by Pt, Co/Al2O4 in the catalyst could be reduced partially even at 923 K, the temperature of pre‐reduction for the reaction, confirmed by TPR. Based on these results, it was considered that the zerovalent platinum with high dispersion over the catalyst surface and the zerovalent cobalt resulting from Co/Al2O4 reduction are responsible for high activity of the Pt‐Co/Al2O3 catalyst, and the remain Co/Al2O4 is beneficial to suppression of carbon deposition over the catalyst.  相似文献   

11.
The development of active, selective, and robust catalysts is a key issue in promoting the practical application of hydrazine monohydrate (N2H4 ? H2O) as a viable hydrogen carrier. Herein, the synthesis of a supported Ni–Pt bimetallic nanocatalyst on mesoporous ceria by a one‐pot evaporation‐induced self‐assembly method is reported. The catalyst exhibits exceptionally high catalytic activity, 100 % selectivity, and satisfactory stability in promoting H2 generation from an alkaline solution of N2H4 ? H2O at moderate temperatures. For example, the Ni60Pt40/CeO2 catalyst enabled complete decomposition of N2H4 ? H2O to generate H2 at a rate of 293 h?1 at 30 °C in the presence of 2 M NaOH, which compares favorably with the reported N2H4 ? H2O decomposition catalysts. Phase/structural analysis by XRD, TEM, and Auger electron spectroscopy was conducted to gain insight into the excellent catalytic performance of the Ni–Pt/CeO2 catalyst.  相似文献   

12.
A novel Pt–TiO2/Ag nanotube photocatalyst has been synthesized successfully via a facile method. TiO2 nanotubes are assembled with numerous ultrathin TiO2 nanosheets and show a highly open structure. The gaps between adjacent TiO2 nanosheets can serve as channels for the access of reactants, accelerating the mass transfer process. During the fabrication process of the Pt–TiO2/Ag nanotube photocatalyst, high‐quality Pt–SiO2 nanotubes are synthesized first with the structure‐directing effect of polyvinylpyrrolidone. Then a TiO2 layer is coated on the outside surface of the silica nanotubes. The introduced titanium species can be converted into TiO2 nanosheet structure during the subsequent hydrothermal treatment, gradually constructing nanosheet‐assembled nanotubes. Lastly, after the introduction of another electron sink function site of Ag through UV irradiation, the Pt–TiO2/Ag nanotube photocatalyst with dual electron sink functional sites is obtained. The specially doped Pt and Ag NPs can simultaneously inhibit the recombination process of photogenerated charge carriers and increase light utilization efficiency. Therefore, the as‐synthesized Pt–TiO2/Ag nanotube catalyst exhibits a high photocatalytic degradation performance for rhodamine B of 0.2 min?1, which is about 3.2 and 5.3 times as high as that of Pt–TiO2 and TiO2 nanotubes because of the enhanced charge carrier separation efficiency. Furthermore, in the unique nanoarchitecture, the nanotubes are assembled with numerous ultrathin TiO2 nanosheets, which can absorb abundant active species and dye molecules for photocatalytic reaction. On the basis of experimental results, a possible rhodamine B degradation mechanism is proposed to explain the excellent photocatalytic efficiency of the Pt–TiO2/Ag nanotube photocatalyst.  相似文献   

13.
Photo–thermo catalysis, which integrates photocatalysis on semiconductors with thermocatalysis on supported nonplasmonic metals, has emerged as an attractive approach to improve catalytic performance. However, an understanding of the mechanisms in operation is missing from both the thermo‐ and photocatalytic perspectives. Deep insights into photo–thermo catalysis are achieved via the catalytic oxidation of propane (C3H8) over a Pt/TiO2‐WO3 catalyst that severely suffers from oxygen poisoning at high O2/C3H8 ratios. After introducing UV/Vis light, the reaction temperature required to achieve 70 % conversion of C3H8 lowers to a record‐breaking 90 °C from 324 °C and the apparent activation energy drops from 130 kJ mol?1 to 11 kJ mol?1. Furthermore, the reaction order of O2 is ?1.4 in dark but reverses to 0.1 under light, thereby suppressing oxygen poisoning of the Pt catalyst. An underlying mechanism is proposed based on direct evidence of the in‐situ‐captured reaction intermediates.  相似文献   

14.
The metal–organic framework (MOF) [Pd(2‐pymo)2]n (2‐pymo=2‐pyrimidinolate) was used as catalyst in the hydrogenation of 1‐octene. During catalytic hydrogenation, the changes at the metal nodes and linkers of the MOF were investigated by in situ X‐ray absorption spectroscopy (XAS) and IR spectroscopy. With the help of extended X‐ray absorption fine structure and X‐ray absorption near edge structure data, Quick‐XAS, and IR spectroscopy, detailed insights into the catalytic relevance of Pd2+/Pd0 in the hydrogenation of 1‐octene could be achieved. Shortly after exposure of the catalyst to H2 and simultaneously with the hydrogenation of 1‐octene, the aromatic rings of the linker molecules are hydrogenated rapidly. Up to this point, the MOF structure remained intact. After completion of linker hydrogenation, the linkers were also protonated. When half of the linker molecules were protonated, the onset of reduction of the Pd2+ centers to Pd0 was observed and the hydrogenation activity decreased, followed by fast reduction of the palladium centers and collapse of the MOF structure. Major fractions of Pd0 are only observed when the hydrogenation of 1‐octene is almost finished. Consequently, the Pd2+ nodes of the MOF [Pd(2‐pymo)2]n are identified as active centers in the hydrogenation of 1‐octene.  相似文献   

15.
A facile strategy is reported for the fabrication of Pt‐loaded core–shell nanocomposite ellipsoids (Fe2O3‐Pt@DSL) consisting of ellipsoidal Fe2O3 cores, double‐layered La2O3 shells and deposited Pt nanoparticles (NPs). The formation of the doubled‐shelled structure uses Fe2O3‐Pt@mSiO2 as template sacrificial agent and it involves the re‐deposition of silica and self‐assembly of metal oxide units. The preparation methods of double‐shelled metal oxides avoid repeated coating and etching and could be utilized to fabricate other shaped double‐shelled composites. Characterization results indicated that the Fe2O3‐Pt@DSL nanocomposites possessed mesoporous structure and tunable shell thickness. Moreover, due to the formation of Fe2O3 and La2O3 composites, Pt NPs can also be stabilized via deposition on chemically active oxides with a synergistic effect. Therefore, as a catalyst for the reduction of 4‐nitrophenol, Fe2O3‐Pt@DSL showed superior catalytic activity and reusability due to structural superiority and enhanced composite synergy. Finally, well‐dispersed Pt NPs were encapsulated into the void between the shell layers to construct the Fe2O3‐Pt@DSL‐Pt catalyst.  相似文献   

16.
Pt nanoparticles are typically decorated as co‐catalyst on semiconductors to enhance the photocatalytic performance. Due to the low abundance and high cost of Pt, reaching a high activity with minimized co‐catalyst loadings is a key challenge in the field. We explore a dewetting‐dealloying strategy to fabricate on TiO2 nanotubes nanoporous Pt nanoparticles, aiming at improving the co‐catalyst mass activity for H2 generation. For this, we sputter first Pt‐Ni bi‐layers of controllable thickness (nm range) on highly ordered TiO2 nanotube arrays, and then induce dewetting‐alloying of the Pt‐Ni bi‐layers by a suitable annealing step in a reducing atmosphere: the thermal treatment causes the Pt and Ni films to agglomerate and at the same time mix with each other, forming on the TiO2 nanotube surface metal islands of a mixed PtNi composition. In a subsequent step we perform chemical dealloying of Ni that is selectively etched out from the bimetallic dewetted islands, leaving behind nanoporous Pt decorations. Under optimized conditions, the nanoporous Pt‐decorated TiO2 structures show a>6 times higher photocatalytic H2 generation activity compared to structures modified with a comparable loading of dewetted, non‐porous Pt. We ascribe this beneficial effect to the nanoporous nature of the dealloyed Pt co‐catalyst, which provides an increased surface‐to‐volume ratio and thus a more efficient electron transfer and a higher density of active sites at the co‐catalyst surface for H2 evolution.  相似文献   

17.
This paper reports the green and in situ preparation of Fe3O4@SiO2‐Ag magnetic nanocatalyst synthesized using safflower (Carthamus tinctorius L.) flower extract without the addition of any stabilizers or surfactants. The catalytic performance of the resulting nanocatalyst was examined for the reduction of 4‐nitrophenol (4‐NP), methylene blue (MB) and methyl orange (MO) in an environment‐friendly medium at room temperature. The main factors such as pH, temperature and amount of catalyst influencing the nanocatalyst performance were studied. The apparent rate constants for 4‐NP, MO and MB reduction were calculated, being 0.756 min?1, 0.064 s?1 and 0.09 s?1, respectively. The catalyst was recovered using an external magnet and reused several times with negligible loss of catalytic activity. The as‐synthesized nanoparticles were characterized using powder X‐ray diffraction, transmission electron microscopy, UV–visible, Fourier transform infrared and inductively coupled plasma atomic emission spectroscopies, dynamic light scattering and vibrating sample magnetometry.  相似文献   

18.
Nitrones are key intermediates in organic synthesis and the pharmaceutical industry. The heterogeneous synthesis of nitrones with multifunctional catalysts is extremely attractive but rarely explored. Herein, we report ultrasmall platinum nanoclusters (PtNCs) encapsulated in amine‐functionalized Zr metal–organic framework (MOF), UiO‐66‐NH2 (Pt@UiO‐66‐NH2) as a multifunctional catalyst in the one‐pot tandem synthesis of nitrones. By virtue of the cooperative interplay among the selective hydrogenation activity provided by the ultrasmall PtNCs and Lewis acidity/basicity/nanoconfinement endowed by UiO‐66‐NH2, Pt@UiO‐66‐NH2 exhibits remarkable activity and selectivity, in comparison to Pt/carbon, Pt@UiO‐66, and Pd@UiO‐66‐NH2. Pt@UiO‐66‐NH2 also outperforms Pt nanoparticles supported on the external surface of the same MOF (Pt/UiO‐66‐NH2). To our knowledge, this work demonstrates the first examples of one‐pot synthesis of nitrones using recyclable multifunctional heterogeneous catalysts.  相似文献   

19.
One of the biggest obstacles to the dissemination of fuel cells is their cost, a large part of which is due to platinum (Pt) electrocatalysts. Complete removal of Pt is a difficult if not impossible task for proton exchange membrane fuel cells (PEM‐FCs). The anion exchange membrane fuel cell (AEM‐FC) has long been proposed as a solution as non‐Pt metals may be employed. Despite this, few examples of Pt‐free AEM‐FCs have been demonstrated with modest power output. The main obstacle preventing the realization of a high power density Pt‐free AEM‐FC is sluggish hydrogen oxidation (HOR) kinetics of the anode catalyst. Here we describe a Pt‐free AEM‐FC that employs a mixed carbon‐CeO2 supported palladium (Pd) anode catalyst that exhibits enhanced kinetics for the HOR. AEM‐FC tests run on dry H2 and pure air show peak power densities of more than 500 mW cm?2.  相似文献   

20.
Bimetallic tubular nanostructures have been the focus of intensive research as they have very interesting potential applications in various fields including catalysis and electronics. In this paper, we demonstrate a facile method for the fabrication of Au–Pt double‐walled nanotubes (Au–Pt DWNTs). The DWNTs are fabricated through the galvanic displacement reaction between Ag nanowires and various metal ions, and the Au–Pt DWNT catalysts exhibit high active catalytic performances toward both methanol electro‐oxidation and 4‐nitrophenol (4‐NP) reduction. First, they have a high electrochemically active surface area of 61.66 m2 g?1, which is close to the value of commercial Pt/C catalysts (64.76 m2 g?1), and the peak current density of Au–Pt DWNTs in methanol oxidation is recorded as 138.25 mA mg?1, whereas those of Pt nanotubes, Au/Pt nanotubes (simple mixture), and commercial Pt/C are 24.12, 40.95, and120.65 mA mg?1, respectively. The Au–Pt DWNTs show a markedly enhanced electrocatalytic activity for methanol oxidation compared with the other three catalysts. They also show an excellent catalytic performance in comparison with common Au nanotubes for 4‐nitrophenol (4‐NP) reduction. The attractive performance exhibited by these prepared Au–Pt DWNTs can be attributed to their unique structures, which make them promising candidates as high‐performance catalysts.  相似文献   

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