Formation of intermediate intermetallic layers on interaction of electrodeposited Sn,Ni-Fe,Ni-B coatings with different metallic substrata

The structure of layers and formation of intermetallic phases after thermal treatment in the system of thin electrodeposited Sn, Ni-Fe and sputtered Cu, Fe-Ni layers (thickness 0.1-2.0 μm) and thick electrodeposited Sn (thickness 6-10 μm) and Fe-Ni and Ni-B layers (thickness 2 μm) have been investigated by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), and by metallographic and X-ray diffraction (XRD) techniques. The formation of intermetallic phases NiSn₃, Ni₃Sn₂, FeSn₂ and considerable reduction in the formation of brittle layers Ni₃Sn₄, Cu₆Sn₅, Cu₃Sn are determined by the structure and purity of electrodeposited tin [C (0.5-5) x 10-²; N (1-5) x 10-²; Fe, Cu, Bi, Pb (0.15-5.0) x 10^-2 wt%] in the system Sn/Fe-Ni/Cu. Electrodeposited Fe-Ni (80% Ni) as barrier layer in the system Sn/Fe-Ni/sputtered Cu completely prevents formation of Cu₆Sn₅, Cu₃Sn as a result of thermal treatment at 170°C up to 75 h. An amorphous Ni-B layer [B 4-8; C (3-7) x 10^-2 wt%] prevents formation of Ni₃Sn₄ and Cu₆Sn₅ in the system Sn/Ni-B/Cu (or Cu-Zn alloy) as a result of thermal treatment at 130°C (200 h) and 170°C (150 h).     

Solvothermal synthesis and optical limiting properties of carbon nanotube-based hybrids containing ternary chalcogenides

Two or three types of semiconductor nanoparticles (NPs) have been deposited on the sidewalls of multi-wall carbon nanotubes (MWCNTs) by a solvothermal treatment of a mixture containing poly(sodium 4-styrenesulfonate) (PSS) wrapped MWCNTs, metal chloride (CuCl₂ and SnCl₂), and thiourea. Changing the ratio of Cu²⁺ to Sn²⁺ alters the composition of the resultant MWCNT–PSS–NP hybrids. Under Cu/Sn ratios of 3:1 and 2:1, MWCNTs can be simultaneously decorated with Cu₂S and Cu₃SnS₄ NPs. When the ratio is reduced to 1:1, Cu₃SnS₄, Cu₂S and SnO₂ NPs would be formed at the same time. Further decreasing the ratio results in the formation of Cu₂SnS₃ and SnO₂ instead of Cu₃SnS₄ and Cu₂S. Open-aperture z-scan measurements have been carried out on three typical MWCNT–PSS–NP samples to study their optical limiting (OL) properties. The addition of semiconductor NPs can improve the OL performance of MWCNTs, and the composition of the NPs has a significant effect on the OL behavior of the hybrids.     

Performance of CuO/Al2O3 Catalysts Promoted by SnO2 and ZrO2 in the Selective Oxidation of Carbon Monoxide

The effect of added SnO₂ and ZrO₂ to CuO/Al₂O₃ catalysts was investigated with reference to the oxygen spillover phenomena in the selective oxidation of carbon monoxide. The TPR and TPO analyses indicated that SnO₂ and ZrO₂ addition caused oxygen migration and induced the formation of high concentrations of active oxygen species on the SnO₂ and ZrO₂ surface. The catalytic activities of SnO₂ and ZrO₂ supported CuO/Al₂O₃ catalysts were superior to that for CuO/Al₂O₃ catalysts in the selective oxidation of carbon monoxide. Oxygen, when absorbed to the SnO₂ and ZrO₂ surface can spill over to the CuO phase and easily react with carbon monoxide. Consequently, the addition of SnO₂ and ZrO₂ led to significantly improved activities. This can be attributed to the enhanced migration of oxygen to the catalyst surface.     

Improving the Stability and Ethanol Electro‐Oxidation Activity of Pt Catalysts by Selectively Anchoring Pt Particles on Carbon‐Nanotubes‐Supported‐SnO2

To improve the stability and activity of Pt catalysts for ethanol electro‐oxidation, Pt nanoparticles were selectively deposited on carbon‐nanotubes (CNTs)‐supported‐SnO₂ to prepare Pt/SnO₂/CNTs and Pt/CNTs was prepared by impregnation method for reference study. X‐ray diffraction (XRD) was used to confirm the crystalline structures of Pt/SnO₂/CNTs and Pt/CNTs. The stabilities of Pt/SnO₂/CNTs and Pt/CNTs were compared by analyzing the Pt size increase amplitude using transmission electron microscopy (TEM) images recorded before and after cyclic voltammetry (CV) sweeping. The results showed that the Pt size increase amplitude is evidently smaller for Pt/SnO₂/CNTs, indicating the higher stability of Pt/SnO₂/CNTs. Although both catalysts exhibit degradation of electrochemical active surface area (EAS) after CV sweeping, the EAS degradation for the former is lower, further confirming the higher stability of Pt/SnO₂/CNTs. CV and potentiostatic current–time curves were recorded for ethanol electro‐oxidation on both catalysts before and after CV sweeping and the results showed that the mass specific activity of Pt/CNTs increases more than that of Pt/SnO₂/CNTs, indicating that Pt/CNTs experiences more severe evolution and is less stable. The calculated area specific activity of Pt/SnO₂/CNTs is larger than that of Pt/CNTs, indicating SnO₂ can co‐catalyze Pt due to plenty of interfaces between SnO₂ and Pt.     

Preparation of Catalyst Ni–Cu/CNTs by Chemical Reduction with Formaldehyde for Steam Reforming of Methanol

The novel catalyst Ni–Cu alloys supported on carbon nanotubes (CNTs) was prepared by reduction with formaldehyde and applied in steam reforming of methanol. With nitric acid and sulfuric acid to create defects on the surface of CNTs and using ethanol to improve the hydrophilicity of CNTs, the Ni–Cu alloys were anchored on the surface of CNTs by co-reduction of Ni- and Cu-precursors under the use of tetra-n-methylammonium hydroxide to reduce the aggregation of Ni–Cu particles. In contrast, Ni–Cu catalyst supported on activated carbon (Ni–Cu/C) was prepared as well, and the bimetal of Ni and Cu supported on CNTs (Ni/Cu/CNTs) was attained by successive reduction of first Cu- and then Ni-precursors. The catalysts were characterized with XRD, ED, FESEM, transmission electron microscopy, and Thermogravimetric analysis. The hydrogen yield in steam reforming of methanol was near 100% at 360 °C over 20 wt.% Ni₂₀–Cu₈₀/CNTs. The catalytic activity of Ni₂₀–Cu₈₀/CNTs is much higher than that of Ni₂₀–Cu₈₀/C and Ni₂₀/Cu₈₀/CNTs.     

Gas phase hydrogenation of maleic anhydride to γ-butyrolactone by Cu–Zn–Ti catalysts

Cu–Zn–Ti catalysts were prepared by coprecipitation method. The calcined and reduced Cu–Zn–Ti catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction (TPR), and N₂ adsorption. The calcined Cu–Zn–Ti catalysts were composed of CuO, ZnO, and amorphous TiO₂. There were two kinds of CuO species present in the calcined Cu–Zn–Ti catalyst. At a lower copper content, CuO species interacted with ZnO and TiO₂; at a higher copper content, both the surface-anchored and bulk CuO species were present. After reduction, metallic copper (Cu^o) appeared in all Cu–Zn–Ti catalysts. Cu^o produced by reduction of the surface-anchored CuO favored the deep hydrogenation of maleic anhydride. ZnO and TiO₂ had synergistic effect on the catalytic activity of Cu–Zn–Ti catalysts in hydrogenation of maleic anhydride.     

Facile synthesis of single crystalline SnO2 nanowires

Single crystalline SnO₂ nanowires with diameter in the range of 10–100 nm and several micrometers in length have been successfully prepared by the combustion technique in air using Al, Cu₂O and SnO as the raw materials. FE–SEM and TEM images showed that the nanowires were single crystalline, growing along the [310] direction. The nanowires' growth mechanism was suggested to follow both VLS and VS mechanisms. The formation of SnO₂ nanowires underwent three steps: tin vapor generation via combustion synthesis, oxidation of the tin vapor and its nucleation and subsequent growth. At the same time, porous Al₂O₃ ceramic and Cu–Sn alloy were obtained during the combustion synthesis process.     

Tubular Sn-filled carbon nanostructures on ITO: Nanocomposite material for multiple applications

Hollow carbon nanostructures filled by metallic Sn were fabricated by means of chemical vapor deposition on transparent Indium Tin Oxide (ITO). We found no need for catalytic particles, and the growth happens in the temperature range 820–940 K. Upon annealing in an oxygen atmosphere, the carbon skin could be burned out, leaving SnO_x pillars on the ITO substrate. The electrical and optical properties of the grown Sn/C and SnO_x nanopillars were characterized.This growth strategy is versatile and can suitably be adapted to different substrate materials, provided that ITO can be deposited and annealed at the temperature required for the formation of the nanostructures. The rational control of this simple growth process and the lack of deposited external catalysts allow the fabrication of ordered, possibly, vertically aligned nanopillars over large areas, with tunable morphological, electrical and optical characteristics. This approach is envisaged as a promising path to develop energy generation and storage electrodes or chemical sensors with improved efficiency.     

MCM-41 supported CuO/Bi2O3 nanoparticles as potential catalyst for 1,4-butynediol synthesis

CuO/Bi₂O₃ (CuO/Bi₂O₃/MCM-41) nanoparticles supported on MCM-41 were synthesized by a facile impregnation method. The products were characterized by nitrogen adsorption/desorption, X-ray diffraction (XRD), H₂ temperature programmed reduction (H₂-TPR) and scanning electron microscopy (SEM). XRD patterns indicated the presence of crystalline CuO and Bi₂O₃ phase for CuO/Bi₂O₃/MCM-41 catalyst. TPR results revealed CuO nanoparticles were dispersed well on MCM-41. SEM results showed that the nanoparticles were located on the MCM-41. The activity of the catalysts towards ethynylation of formaldehyde for 1,4-butynediol synthesis was evaluated at atmospheric pressure. Compared with unsupported CuO/Bi₂O₃ and commercial Cu/Bi-based catalyst, CuO/Bi₂O₃/MCM-41 catalyst showed maximum conversion (51%) and selectivity (94%) towards 1,4-butynediol. The results show that CuO/Bi₂O₃ catalysts supported on MCM-41 have potential for 1,4-butynediol synthesis in industrial application.     

Single-step polyol synthesis of alloy Pt<Subscript>7</Subscript>Sn<Subscript>3</Subscript> versus bi-phase Pt/SnO<Subscript>x</Subscript> nano-catalysts of controlled size for ethanol electro-oxidation

Disordered alloy and bi-phase PtSn nanoparticles of nominal Pt:Sn ratio of 70:30 atomic % with controlled size and narrow size distribution were synthesized using a single-step polyol method. By adjusting the solution pH it was possible to obtain Pt₇Sn₃ nanoparticles of various sizes from 2.8 to 6.5 nm. We found that the presence of NaOH in the synthesis solution not only influenced the nanoparticle size, but as it was revealed by XRD, it apparently also dictated the degree of Pt and Sn alloying. Three catalysts prepared at lower NaOH concentrations (C_NaOH < 0.15 M) showed disordered alloy structure of the nominal composition, while the other three catalysts synthesized at higher NaOH concentrations (C_NaOH > 0.15 M) consisted of bi-phase nanoparticles comprising a crystalline phase close to that of pure Pt together with an amorphous Sn phase. These observations are plausibly due to the phase separation and formation of monometallic Pt and amorphous SnO_x phases. A proposed reaction mechanism of Pt₇Sn₃ nanoparticle formation is presented to explain these observations along with the catalytic activities measured for the six synthesized carbon-supported Pt₇Sn₃ catalysts. The highest catalytic activity towards ethanol electro-oxidation was found for the carbon-supported bi-phase catalyst that formed the largest Pt (6.5 nm) nanoparticles and SnO_x phase. The second best catalyst was a disordered alloy Pt₇Sn₃ catalyst with the second largest nanoparticle size (5 nm), while catalysts of smaller size (4.5–4.6 nm) but different structure (disordered alloy vs. bi-phase) showed similar catalytic performance inferior to that of the 5 nm disordered alloy Pt₇Sn₃ catalyst. This work demonstrated the importance of producing bi-metallic PtSn catalysts with large Pt surfaces in order to efficiently electro-oxidize ethanol.     

Thermal conversion synthesis of Cu2O photocathode and the promoting effects of carbon coating

Simplifying the synthesis of cuprous oxide (Cu₂O) photocathode has turned out to be critical for scalable application. Herein, we present a novel thermal conversion approach to synthesize a shell/core structured Cu₂O/Cu photocathode. In this method a shell comprising a mixture of CuO and Cu₂O is obtained by heating Cu mesh at 500 °C in air beforehand, and subsequent annealing in N₂ atmosphere converts the unwanted CuO into Cu₂O gradually, which results in the desired Cu₂O/Cu structure. A slightly viscous starch sol coats the Cu₂O shell as carbon source, after carbonizing under N₂ atmosphere, the Cu₂O/Cu is covered with compact carbon films, i.e. C/Cu₂O/Cu. Photoelectrochemical experiments reveal that the introduction of carbon layers on Cu₂O enhances the photocurrent density from − 1.5 to − 2.75 mA·cm^− 2 at 0 V vs. reversible hydrogen electrode (RHE). Moreover, the deposition of carbon films on Cu₂O in this work has little effect on improving the stability.     

Highly conductive polymer composites with excellent toughness,fluidity and temperature-independent conductivity

Conductive polymer composites of low melting point metal/ high melting point metal/polymer were prepared by melt mixing and investigated the effects of Sn-to-Cu content ratio on the microstructure and properties of Sn/Cu/PA6 ternary composites with a metal content of 53.3 vol %. The results show that Sn reacts with Cu to form intermetallic compounds during melting processing. When V_Sn/V_Cu is less than 1.5, the metal phase is a solid. However, if V_Sn/V_Cu is higher than 1.5, the metal phase is a suspension. As V_Sn/V_Cu increases, the morphology of metal phase changes from “islands” to physically continuous networks, and the Volume resistivity, impact strength and complex viscosity of the composites can reach 1.11 × 10⁻⁴ Ω cm, 3.8 kJ/m² and 2.4 × 10³ Pa s, respectively. Moreover, the resistivity of the composites with physically continuous networks is almost independent of temperature. The combination of low and high melt point metals can be considered as a useful strategy to prepare conductive polymer composites with high performance. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48820.     

Preparation of Sn2Sb alloy encapsulated carbon microsphere anode materials for Li-ion batteries by carbothermal reduction of the oxides

A novel process was proposed to prepare Sn₂Sb-encapsulated carbon microspheres (CM/Sn₂Sb) anode materials by inverse emulsion polymerization of resorcinol-formaldehyde (RF) performed in the presence of Sb₂O₃ and SnO₂ powders (1/4 molar ratio), followed by carbonization and carbothermal reduction in an inert atmosphere. The oxides powder were encapsulated within the carbon gel microspheres and the elemental Sn and Sb were reduced from their oxides by the carbonized RF gel to form crystalline Sn₂Sb alloy within carbon microspheres. The CM/Sn₂Sb presented much better cyclability than that of Sn₂Sb alloy powder. The proposed process paves an effective way to prepare high performance Sn₂Sb/C microspheres composite anode materials for lithium-ion batteries.     

Controlled Synthesis of Pt3Sn/C Electrocatalysts with Exclusive Sn–Pt Interaction Designed for Use in Direct Methanol Fuel Cells

Alloy-type Sn–Pt/C electrocatalysts with Pt/Sn = 1.8–3.0 ratios and exclusive Sn–Pt interaction have been prepared by means of controlled surface reactions (CSRs). As demonstrated by XRD, the incorporation of Sn onto Pt/C was achieved satisfactorily yielding a near-stoichiometric fcc Pt₃Sn alloy phase along with a certain amount of the Pt_(1 ? x)Sn_x solid solution. The content and dispersion of the fcc Pt₃Sn phase within the electrocatalysts can be controlled by tuning the reaction conditions of CSRs. No evidence of the presence of SnO₂ phases in the Sn-modified Pt/C samples was found by means of the XRD and EDS analysis. According to in situ XPS studies, the pre-treatment in hydrogen at 350 °C resulted in complete reduction of tin to Sn⁰. These results demonstrate that the method of CSRs is a powerful tool to create of Pt–Sn bimetallic nanoparticles exclusively, without tin introduction onto the carbon support. The performance of the intermetallic SnPt/C catalysts in the CO and methanol electrooxidation reactions depends on the actual composition of the exposed surface and the size of bimetallic particles. In the consecutive tin introduction the decrease of the amount of SnEt₄ precursor added per period, accompanied with an increase of the number of anchoring periods, resulted in an increase of the activity in both electrooxidation reactions as a consequence of an optimal balance of Pt/C ratio, the content of fcc Pt₃Sn phase and metal particle size. It was demonstrated that the increasing tin content above a certain (optimal) amount gives rise to a negative effect on the catalyst performance in the CO and methanol electrooxidation.     

Sintering behaviour of CuO-doped SnO2

The sintering behaviour of CuO-doped SnO₂ ceramics was studied. Additive-free SnO₂ materials do not densify after heat treatment to 1400°C, whereas materials doped with 0.5–0.75 wt.% CuO densify to 98% of theoretical. Copper oxides (CuO/Cu₂O) experience reduction and re-oxidation phenomena. There is no evidence of high vaporisation of SnO₂, nor of liquid formation at low temperature (<1000°C) in the CuO–SnO₂ system. This suggests that CuO acts by grain-boundary mechanisms.     

Structure Characteristics and NO Selective Catalytic Reduction Property of Sn x Zr1-x O2 Solid Solution Catalysts

Novel catalysts, Sn_xZr_1-xO₂ solid solutions, for NO selective catalytic reduction:NO SCR) are reported. They have much higher activity and selectivity than SnO₂ and ZrO₂. Sn⁴⁺ is the main reductive sites as proved by TPR. The dilution of Sn sites by the coexisting Zr causes a suppression of propene combustion and consequently promoted the selective reduction of NO. The rutile structure might be beneficial to NO SCR.     

CO tolerance and catalytic activity of Pt/Sn/SnO2 nanowires loaded on a carbon paper

Electrochemical activities and structural features of Pt/Sn catalysts supported by hydrogen-reduced SnO₂ nanowires (SnO₂NW) are studied, using cyclic voltammetry, CO stripping voltammetry, scanning electron microscopy, and X-ray diffraction analysis. The SnO₂NW supports have been grown on a carbon paper which is commercially available for gas diffusion purposes. Partial reduction of SnO₂NW raises the CO tolerance of the Pt/Sn catalyst considerably. The zero-valence tin plays a significant role in lowering the oxidation potential of CO_ads. For a carbon paper electrode loaded with 0.1 mg cm⁻² Pt and 0.4 mg cm⁻² SnO₂NW, a conversion of 54% SnO₂NW into Sn metal (0.17 mg cm⁻²) initiates the CO_ads oxidation reaction at 0.08 V (vs. Ag/AgCl), shifts the peak position by 0.21 V, and maximizes the CO tolerance. Further reduction damages the support structure, reduces the surface area, and deteriorates the catalytic activity. The presence of Sn metal enhances the activities of both methanol and ethanol oxidation, with a more pronounced effect on the oxidation current of ethanol whose optimal value is analogous to those of PtSn/C catalysts reported in literature. In comparison with a commercial PtRu/C catalyst, the optimal Pt/Sn/SnO₂NW/CP exhibits a somewhat inferior activity toward methanol, and a superior activity toward ethanol oxidation.     

Comparative Study on Catalytic Properties for Low-Temperature CO Oxidation of Cu/CeO2 and CuO/CeO2 Prepared via Solvated Metal Atom Impregnation and Conventional Impregnation

Cu/CeO₂ and CuO/CeO₂ catalysts were prepared by solvated metal atom impregnation (SMAI) and conventional impregnation (CI) and used for carbon monoxide oxidation in CO and air. The catalysts were characterized by means of XRD, XPS, AES and H₂-TPR techniques. The Cu/CeO₂ catalyst prepared via SMAI exhibits higher catalytic activity in CO oxidation than that prepared via CI with the same Cu content due to the smaller Cu particles. The CuO/CeO₂ catalyst prepared via SMAI also shows higher catalytic activity than that prepared via CI because the CuO particles of the former are smaller than the latter and can be reduced by CO more easily. The Cu/CeO₂ catalysts display higher catalytic activities than CuO/CeO₂ catalysts with the same Cu content and prepared by the same method. The TPR profile for CuO/CeO₂ catalyst prepared via SMAI has a single peak, indicating a one-step reduction, whereas the TPR profile for CuO/CeO₂ catalyst prepared via CI has two peaks, indicating a two-step reduction due to the existence of two kinds of CuO species.     

Purity-controllable growth of bamboo-like multi-walled carbon nanotubes over copper-based catalysts

The growth of bamboo-like multi-walled carbon nanotubes (CNTs) without the formation of amorphous carbons was performed using copper-based catalysts by catalytic chemical vapour deposition (CVD) with diluted ethylene at 700–900 °C. The as-grown CNT soot was characterised by transmission electron microscopy, thermogravimetric analysis and Raman spectroscopy. The weak metal–support interaction of a sulphate-assisted copper catalyst (CuSO₄/SiO₂) can provide high-purity growth with remarkable yields of CNTs (2.24–6.10 CNT/g Cu·h) at 850–900 °C. Additionally, hydrogen-assisted CVD can activate inert copper catalysts, e.g., Cu(NO₃)₂/SiO₂ or Cu(CH₃COO)_2/SiO₂, for the growth of CNTs.     

Effect of TiO2 nanoparticles on the horizontal hardness properties of Sn-3.0Ag-0.5Cu-1.0TiO2 composite solder

The improvement in the hardness of Sn-3.0Ag-0.5Cu solder alloy reinforced with 1.0 wt % TiO₂ nanoparticles was evaluated by nanoindentation. A specific indentation array was performed on four different horizontal cross sections of the composite solder with different heights and diameters, in order to verify the mixing homogeneity of TiO₂ nanoparticles within the Sn-3.0Ag-0.5Cu solder paste during the ball milling process. The phase analysis indicated successful blending of the Sn-3.0Ag-0.5Cu with the TiO₂ nanoparticles. According the scanning electron microscopy micrographs, presence of the TiO₂ nanoparticles reduced the size of the Cu₆Sn₅ and Ag₃Sn intermetallic compound phases. Incorporation of the 1.0 wt % TiO₂ nanoparticles improved the hardness values up to 26.2% than that of pure SAC305. The hardness values increased gradually from the top cross sections towards adjacent to the solder/substrate interface. The mechanism of the hardness improvement attained by the TiO₂ nanoparticles addition were also investigated on the horizontal cross sections of the samples.