Atomic Carbon Layers Supported Pt Nanoparticles for Minimized CO Poisoning and Maximized Methanol Oxidation

Maximizing activity of Pt catalysts toward methanol oxidation reaction (MOR) together with minimized poisoning of adsorbed CO during MOR still remains a big challenge. In the present work, uniform and well‐distributed Pt nanoparticles (NPs) grown on an atomic carbon layer, that is in situ formed by means of dry‐etching of silicon carbide nanoparticles (SiC NPs) with CCl₄ gas, are explored as potential catalysts for MOR. Significantly, as‐synthesized catalysts exhibit remarkably higher MOR catalytic activity (e.g., 647.63 mA mg^?1 at a peak potential of 0.85 V vs RHE) and much improved anti‐CO poisoning ability than the commercial Pt/C catalysts, Pt/carbon nanotubes, and Pt/graphene catalysts. Moreover, the amount of expensive Pt is a few times lower than that of the commercial and reported catalyst systems. As confirmed from density functional theory (DFT) calculations and X‐ray absorption fine structure (XAFS) measurements, such high performance is due to reduced adsorption energy of CO on the Pt NPs and an increased amount of adsorbed energy OH species that remove adsorbed CO fast and efficiently. Therefore, these catalysts can be utilized for the development of large‐scale and industry‐orientated direct methanol fuel cells.     

A facile method for preparation of high performance Pt catalyst supported on multi-wall carbon nanotubes for methanol electrooxidation

Due to the inherent inertness of multi-wall carbon nanotubes (MWCNTs), complicated procedures are involved in the preparation of MWCNT-supported catalysts. In this paper, a facile and effective method is introduced to prepare Pt nanoparticles dispersed on the surface of purified MWCNTs. In this method, sodium phthalate (SP) is used as a special additive to function as an effective cross linker between MWCNTs and Pt ions, and ethylene glycol (EG) aqueous solution is used as an effective solvent. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) analyses reveal that the prepared face-centered cubic Pt nanoparticles with the average diameter of 2.2 nm are well dispersed on the surface of the MWCNTs. Cyclic voltammetry and chronoamperometry tests demonstrate that the Pt/MWCNTs catalyst obtained from typical experiment exhibits better catalytic activity and stability for methanol electrooxidation than the Pt catalyst supported on conventional acid-treated MWCNTs (AO-MWCNTs) and JM commercial 20% Pt/C catalyst.     

Small-sized tungsten nitride anchoring into a 3D CNT-rGO framework as a superior bifunctional catalyst for the methanol oxidation and oxygen reduction reactions

The application of direct methanol fuel cells (DMFC) is hampered by high cost, low activity, and poor CO tolerance by the Pt catalyst. Herein, we designed a fancy 3D hybrid by anchoring tungsten nitride (WN) nanoparticles (NPs), of about 3 nm in size, into a 3D carbon nanotube-reduced graphene oxide framework (CNT-rGO) using an assembly route. After depositing Pt, the contacted and strongly coupled Pt–WN NPs were formed, resulting in electron transfer from Pt to WN. The 3D Pt–WN/CNT-rGO hybrid can be used as a bifunctional electrocatalyst for both methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR). In MOR, the catalysts showed excellent CO tolerance and a high mass activity of 702.4 mA·mg_Pt ^–1, 2.44 and 3.81 times higher than those of Pt/CNT-rGO and Pt/C(JM) catalysts, respectively. The catalyst also exhibited a more positive onset potential (1.03 V), higher mass activity (151.3 mA·mg_Pt ^–1), and better cyclic stability and tolerance in MOR than ORR. The catalyst mainly exhibited a 4e-transfer mechanism with a low peroxide yield. The high activity was closely related to hybrid structure. That is, the 3D framework provided a favorable path for mass-transfer, the CNT-rGO support was favorable for charge transfer, and strongly coupled Pt–WN can enhance the catalytic activity and CO-tolerance of Pt. Pt–WN/CNT-rGO represents a new 3D catalytic platform that is promising as an electrocatalyst for DMFC because it can catalyze both ORR and MOR in an acidic medium with good stability and highly efficient Pt utilization.

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Chemical fluid deposition of monometallic and bimetallic nanoparticles on ordered mesoporous silica as hydrogenation catalysts

A simple and green method of depositing monometallic (Ru, Rh, Pd) and bimetallic nanoparticles (Ru-Rh, Ru-Pd and Rh-Pd) on an ordered mesoporous silica support (MCM-41) in supercritical carbon dioxide (scCO2) is described. Metal acetylacetonates were used in the experiments as CO2-soluble metal precursors. Suitable temperature and pressure conditions for synthesizing each kind of nanoparticles were applied in this study. The characterizations of these nanocomposites were performed by transmission electron microscopy (TEM), X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDS). The nanoparticles had average sizes varying from 2 nm to 8 nm. The Ru nanoparticles were clearly shown to be inside the mesopores of MCM-41 from the TEM image. These nanocomposites used as catalysts for hydrogenation was demonstrated. The efficiency of the scCO2 prepared Ru/MCM-41 catalyst was nearly 8 times than that of a Ru/MCM-41 catalyst prepared by conventional impregnation method.     

Memory characteristics of a self-assembled monolayer of Pt nanoparticles as a charge trapping layer

A self-assembled monolayer of Pt nanoparticles (NPs) was studied as a charge trapping layer for non-volatile memory (NVM) applications. Pt NPs with a narrow size distribution (diameter ～4?nm) were synthesized via an alcohol reduction method. The monolayer of these Pt NPs was immobilized on a SiO(2) substrate using poly(4-vinylpyridine) (P4VP) as a surface modifier. A metal-oxide-semiconductor (MOS) type memory device with Pt NPs exhibits a relatively large memory window of 5.8?V under ± 7?V for program/erase voltage. These results indicate that the self-assembled Pt NPs can be utilized for NVM devices.     

Multifunctional Ir–Ru alloy catalysts for reversal-tolerant anodes of polymer electrolyte membrane fuel cells

To address the problem of fuel starvation in fuel-cell electric vehicles,which causes cell voltage reversal and results in cell failure when repeated continuously,we developed a reversal-tolerant anode(RTA) to promote water oxidation in preference to carbon corrosion.Graphitized carbon-supported Ir-Ru alloys with different compositions are employed as RTA catalysts in an acidic polyol solution and are shown to exhibit composition-dependent average crystallite sizes of <5.33 nm.The adopted approach allows the generation of relatively well-dispersed Ir-Ru alloy nanoparticles on the carbon support without severe agglomeration.The activity of IrRu₂/C for the hydrogen oxidation reaction is 1.10 times that of the stateof-the-art Pt/C catalyst.Cell reversal testing by simulation of fuel starvation reveals that the durability of IrRu₂/C(~7 h) significantly exceeds that of the conventional Pt/C catalyst(~10 min) and is the highest value reported so far.Thus,the developed Ir-Ru alloy catalyst can be used to fabricate practical RTAs and replace Pt catalysts in the anodes of polymer electrolyte membrane fuel cells.     

Preparation of a platinum electrocatalyst by coaxial pulse arc plasma deposition

We have developed a new method of preparing Pt electrocatalysts through a dry process. By coaxial pulse arc plasma deposition (CAPD), highly ionized metal plasma can be generated from a target rod without any discharged gases, and Pt nanoparticles can be deposited on a carbon support. The small-sized Pt nanoparticles are distributed over the entire carbon surface. From transmission electron microscopy (TEM), the average size of the deposited Pt nanoparticles is estimated to be 2.5 nm, and their size distribution is narrow. Our electrocatalyst shows considerably improved catalytic activity and stability toward methanol oxidation reaction (MOR) compared with commercially available Pt catalysts such as Pt black and Pt/carbon (PtC). Inspired by its very high efficiency toward MOR, we also measured the catalytic performance for oxygen reduction reaction (ORR). Our PtC catalyst shows a better performance with half-wave potential of 0.87 V, which is higher than those of commercially available Pt catalysts. The higher performance is also supported by a right-shifted onset potential. Our preparation is simple and could be applied to other metallic nanocrystals as a novel platform in catalysis, fuel cells and biosensors.     

Growth of CNTs on Fe-Si catalyst prepared on Si and Al coated Si substrates

In this paper we report the effect of Al interlayers on the growth characteristics of carbon nanotubes (CNTs) using as-deposited and plasma etched Fe-Si catalyst films as the catalysts. Al interlayers having various thicknesses ranging from 2 to 42?nm were deposited on Si substrates prior to the deposition of Fe-Si catalysts. It was found that the Al interlayer diffuses into the Fe-Si catalyst during the plasma etching prior to the CNT growth, leading to the swelling and amorphization of the catalyst. This allows enhanced carbon diffusion in the catalyst and therefore a faster growth rate of the resulting CNTs. It was also found that use of an Al interlayer having a thickness of ～3 ± 1?nm is most effective. Due to the effectiveness of this, the normally required catalyst etching is no longer needed for the growth of CNTs.     

Preparation of a platinum electrocatalyst by coaxial pulse arc plasma deposition

Abstract

We have developed a new method of preparing Pt electrocatalysts through a dry process. By coaxial pulse arc plasma deposition (CAPD), highly ionized metal plasma can be generated from a target rod without any discharged gases, and Pt nanoparticles can be deposited on a carbon support. The small-sized Pt nanoparticles are distributed over the entire carbon surface. From transmission electron microscopy (TEM), the average size of the deposited Pt nanoparticles is estimated to be 2.5 nm, and their size distribution is narrow. Our electrocatalyst shows considerably improved catalytic activity and stability toward methanol oxidation reaction (MOR) compared with commercially available Pt catalysts such as Pt black and Pt/carbon (PtC). Inspired by its very high efficiency toward MOR, we also measured the catalytic performance for oxygen reduction reaction (ORR). Our PtC catalyst shows a better performance with half-wave potential of 0.87 V, which is higher than those of commercially available Pt catalysts. The higher performance is also supported by a right-shifted onset potential. Our preparation is simple and could be applied to other metallic nanocrystals as a novel platform in catalysis, fuel cells and biosensors.     

Hollow MCM-41 microspheres derived from P(St-MMA)/MCM-41 core/shell composite particles

In soap-free latex media, poly(styrene-methyl methacrylate)/MCM-41 core/shell composite microspheres have been fabricated by adding silicate source in batches. In this process, silicate species and the surfactant micelles were self-assembled into 2-dimensional hexagonal arrangement on the surface of P(St-MMA) microspheres. Hollow MCM-41 microspheres were obtained via removing polymer core by solvent. XRD, TEM, IR and N₂ adsorption-desorption analysis were applied to characterize products. The results showed that average diameter and wall thickness of hollow MCM-41 microspheres is about 240 nm and 20 nm, respectively. Results of N₂ adsorption-desorption indicate that hollow MCM-41 microspheres possess a highly ordered mesoporous structure and a narrow pore distribution with a mean value of 2.34 nm.     

磁性MCM-41分离回收RT培司废水中四甲基氢氧化铵的研究

硝基苯法合成RT培司(4-氨基二苯胺)的废水色度高、组分复杂、催化剂四甲基氢氧化铵(TMAOH)难以分离回收。提出采用磁性MCM-41对RT培司废水中有机副产物进行选择性吸附分离。制备的磁性MCM-41样品采用X射线衍射仪(XRD)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)、N₂吸附-脱附和振动样品磁场计(VSM) 等手段进行表征。结果表明, 磁性MCM-41颗粒的粒径范围为200~300 nm, BET比表面积约为655.2 m²/g, 孔径分布为0.5~4 nm, 内核铁酸镍的存在使磁性MCM-41具有超顺磁性。吸附研究表明磁性MCM-41对RT培司废水中吩嗪、偶氮苯和苯胺等有机物具有良好吸附作用, 经5次吸附磁分离后, RT培司废水中四甲基氢氧化铵能够达到回用要求, 吸附后的磁性MCM-41在外加磁场下极易分离。     

羟基锡酸盐载铂复合催化剂Pt/(Co,Zn)Sn(OH)6的合成及其甲醇电催化氧化性能

以羟基锡酸盐CoSn（OH）₆和ZnSn（OH）₆纳米空心立方体为前体,采用抗坏血酸作为弱还原剂,经过超声过程分别合成了羟基锡酸钴载Pt/CoSn（OH）₆和羟基锡酸锌载Pt/ZnSn（OH）₆复合催化剂,并在甲醇氧化反应（MOR）中表现出良好的性能。Pt/CoSn（OH）₆和Pt/ZnSn（OH）₆催化剂的单位质量活性分别为1 095.6 mA/mg和699.5 mA/mg,高于C载Pt（Pt/C）的594.6 mA/mg。利用XRD、SEM、TEM、XPS和电化学测试对催化剂晶体结构和性能间的关系进行了探索。CO溶出实验结果表明,羟基锡酸盐载体有利于Pt表面CO的去除,载体与Pt间的强相互作用和载体表面的大量羟基基团增强了催化剂的催化活性和CO抗毒性。此外,Pt/（Co,Zn）Sn（OH）₆催化剂中单质Pt高的相对含量也有利于提高MOR活性。通过研究载铂羟基锡酸盐电催化氧化甲醇性能,能够揭示载体结构对催化性能的影响,有助于羟基锡酸盐载铂复合催化剂在直接甲醇燃料电池（DMFCs）领域的应用。     

Biosynthesis of waste pistachio shell supported silver nanoparticles for the catalytic reduction processes

Silver nanoparticles (NPs) are immobilised on pistachio shell surface by Cichorium intybus L. leaves extract as an antioxidant media. The Fourier transform infrared spectra, X‐ray diffraction, field‐emission scanning electron microscopy equipped with energy‐dispersive X‐ray spectroscopy, and transmission electron microscope analyses confirmed the support of silver NPs on the pistachio shell (Ag NPs/pistachio shell). Ag NPs on the pistachio shell had a diameter basically in the 10–15 nm range. Reduction reactions of 4‐nitrophenol (4‐NP), and organic dyes at ambient condition were used in the investigation of the catalytic performance of the prepared catalyst. Through this research, the Ag NPs/pistachio shell shows a high activity and recyclability, and reusability without loss of its catalytic activity.Inspec keywords: transmission electron microscopy, nanoparticles, X‐ray diffraction, catalysis, nanofabrication, dyes, X‐ray chemical analysis, reduction (chemical), silver, catalysts, Fourier transform infrared spectra, field emission scanning electron microscopyOther keywords: waste pistachio shell, silver nanoparticles, catalytic reduction processes, pistachio shell surface, antioxidant media, infrared spectra, X‐ray diffraction, field‐emission scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, transmission electron microscope analyses, reduction reactions, catalytic performance, catalytic activity, Cichorium intybus L. leaves extract, size 10.0 nm to 15.0 nm, Ag     

Preparation of highly dispersed tungsten oxide on MCM-41 via atomic layer deposition and its application to butanol dehydration

Highly dispersed tungsten oxide on MCM-41 was synthesized using a novel atomic layer deposition (ALD) method. BET, XRD, XPS, NH3-TPD, and pyridine-IR were used to study the physicochemical properties of the supported tungsten oxides. In this study, the maximum loading of tungsten oxide on MCM-41 that could be prepared using the modified ALD method was 27.0 wt%. It was confirmed that the textural properties of the mesoporous silica were maintained after tungsten oxide loading. The NH3-TPD and Py-IR results indicated that weak acid sites, mainly Lewis acid sites, were produced over the WO3/MCM-41 samples. Moreover, 2-butanol dehydration was performed to demonstrate the potential advantages of the WO3/MCM-41 catalysts. The WO3/MCM-41 catalyst with 27.0 wt% tungsten oxide loading showed the highest activity in the dehydration of 2-butanol, which was attributed to the highest overall number of acid sites among the WO3/MCM-41 catalysts. The highly dispersed tungsten oxide on MCM-41 prepared via ALD can be an effective catalyst for producing butenes through 2-butanol dehydration.     

Pt/C催化剂制备及CO催化氧化性能研究

采用大气压介质阻挡放电辅助氢气热还原方法和氢气热还原方法制备Pt/C催化剂,考察了制备方法及Pt负载量对Pt/C催化性能的影响。采用X-射线衍射(XRD)、循环伏安法、CO催化氧化反应研究Pt/C催化剂的晶相结构、电催化性能和CO催化氧化活性。结果表明:大气压介质阻挡放电辅助氢气热还原所制备的样品具有更高的电化学活性和CO催化氧化活性。当Pt负载量在2%到10%之间变化时,Pt/C-PC催化活性随负载量增加而增加。XRD测试结果显示当Pt负载量为2%,5%和10%时,Pt粒径分别为:10.6 nm,9.1 nm和6.4 nm,说明采用等离子体辅助氢气热还原方法制备的Pt/C-PC催化剂,Pt负载量越大,Pt粒径越小,CO催化氧化活性更高。     

杂多酸固载催化剂的合成及窄分子量纤维素制备的研究

通过水热合成法制备MCM-41型介孔分子筛,采用浸渍法负载磷钨酸于MCM-41介孔分子筛中,煅烧得到新型HPW/MCM-41固载催化剂。利用傅里叶红外光谱(FT-IR)、X射线衍射(XRD)、热重分析(TG)和扫描电镜(SEM)对固载催化剂进行表征;考察催化剂对棉纤维催化降解反应的性能。结果表明,新型HPW/MCM-41固载催化剂即持有了磷钨酸的Keggin结构,同时又保持了分子筛的完整介孔结构,具有催化、筛分双重性能。棉纤维催化降解反应数据显示,磷钨酸负载量、反应温度、催化剂用量、液固比及停留时间均影响HPW/MCM-41降解纤维素的性能。在单因素实验最佳反应条件下,棉纤维素降解产物的分子量分布较为均匀,降解产物的产率较优。     

Enhanced catalytic performances of Ag nanoparticles supported on layered double hydroxide for styrene epoxidation

Catalysts or support to catalysts based on layered double hydroxides (LDHs) have been widely investigated in the last few years. Supported Au nanoparticles (NPs), prepared typically by a homogeneous deposition–precipitation technique, have been utilized as catalysts with high activity and selectivity for styrene epoxidation. We herein present a preparation of chemically reduced and cost-saving Ag NPs on the LDH support used as catalyst for styrene epoxidation. A proper reaction condition is optimized, for example, a loading of 2.67 wt% Ag, a conversion temperature of 82 °C, and a conversion time of 8 h. The Ag/LDH catalyst exhibits enhanced reaction selectivity and product yield in comparison with the Au/LDH reported previously. Our results may initiate a facile framework appropriate for noble metallic NPs supported on layered inorganic crystal compounds.     

Ultrathin Co-N-C Layer Modified Pt–Co Intermetallic Nanoparticles Leading to a High-Performance Electrocatalyst toward Oxygen Reduction and Methanol Oxidation

The development of low platinum-based alloy electrocatalysts is crucial to accelerate the commercialization of fuel cells, yet remains a synthetic challenge and an incompatibility between activity and stability. Herein, a facile procedure to fabricate a high-performance composite that comprises Pt–Co intermetallic nanoparticles (IMNs) and Co, N co-doped carbon (Co-N-C) electrocatalyst is proposed. It is prepared by direct annealing of homemade carbon black-supported Pt nanoparticles (Pt/KB) covered with a Co-phenanthroline complex. During this process, most of Co atoms in the complex are alloyed with Pt to form ordered Pt–Co IMNs, while some Co atoms are atomically dispersed and doped in the framework of superthin carbon layer derived from phenanthroline, which is coordinated with N to form Co–N_x moieties. Moreover, the Co-N-C film obtained from complex is observed to cover the surface of Pt–Co IMNs, which prevent the dissolution and agglomeration of nanoparticles. The composite catalyst exhibits high activity and stability toward oxygen reduction reactions (ORR) and methanol oxidation reactions (MOR), delivering outstanding mass activities of 1.96 and 2.92 A mg_Pt⁻¹ for ORR and MOR respectively, owing to the synergistic effect of Pt–Co IMNs and Co-N-C film. This study may provide a promising strategy to improve the electrocatalytic performance of Pt-based catalysts.     

First-principles calculations of the dissolution and coalescence properties of Pt nanoparticle ORR catalysts: The effect of nanoparticle shape

The degradation of Pt nanoparticles (NPs) in fuel cell cathodes leads to the loss of the precious metal catalyst. While the effect of NP size on Pt dissolution has been studied extensively, the influence of NP shape is largely unexplored. Because of the recent development of experimental methods to control the shape of metal NPs, rational guidelines/insights on the shape effects on NP stability are imperative. In this study, first-principles calculations based on density functional theory were conducted to determine the stability of 1–2 nm Pt NPs against Pt dissolution and coalescence with respect to NP shape. Toward dissolution, the stability of the Pt NPs increases in the following order: Hexagonal close-packed < icosahedral < cuboctahedral < truncated octahedral. This trend is attributed to the synergy of the oxygen adsorption strength and the local coordination of the Pt atoms. With respect to coalescence, the size of a NP is related to its propensity to coalesce or detach/migrate to form larger particles. The stability of the Pt NPs was found to increase in the following order: Hexagonal close-packed < truncated octahedral < cuboctahedral < icosahedral, and was correlated with the cohesive energies of the particles. By combining the characteristic stabilities of the shapes, new “metal-interfaced” Pt-based coreshell architectures were proposed that should be more stable than pure Pt nanoparticles with respect to both dissolution and coalescence.

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Galvanic Replacement–Mediated Synthesis of Ni‐Supported Pd Nanoparticles with Strong Metal–Support Interaction for Methanol Electro‐oxidation

Herein, well‐defined Pd nanoparticles (NPs) developed on Ni substrate (Pd NPs/Ni) are synthesized via a facile galvanic replacement reaction (GRR) route performed in ethaline‐based deep eutectic solvent (DES). For comparison, a Pd NPs/Ni composite is also prepared by the GRR method conducted in an aqueous solution. The Pd NPs/Ni obtained from the ethaline‐DES is catalytically more active and durable for the methanol electro‐oxidation reaction (MOR) than those of the counterpart derived from conventional aqueous solution and commercial Pd/C under alkaline media. Detailed kinetic analysis indicates that the unique solvent environment offered by ethaline plays vital roles in adjusting the reactivity of the active species and their mass transport properties to control over the genesis of the Pd NPs/Ni nanocomposite. The resulting Pd NPs/Ni catalyst possesses a homogeneous dispersion of Pd NPs with a strong Pd (metal)–Ni (support) interaction. This structure enhances the charge transfer between the support and the active phases, and optimizes the adsorption energy of OH^? and CO on the surface, leading to superior electrocatalytic performance. This work provides a novel GRR strategy performed in ethaline‐DES to the rational design and construction of advanced metal/support catalysts with strong interaction for improving the activity and durability for MOR.