Influence of Preparation Modes on Pt–Ni/CNTs Catalysts Used in the Selective Hydrogenation of Cinnamaldehyde to Hydrocinnamaldehyde

Pt–Ni/CNTs catalysts are prepared by different impregnation techniques and different reduction methods (H₂, HCHO, and KBH₄) for the selective hydrogenation of cinnamaldehyde (CMA) to hydrocinnamaldehyde (HCMA) and investigated by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and temperature programmed reduction (H₂-TPR) techniques. The results show that the catalytic selectivity and activity of the Pt–Ni/CNTs catalysts would significantly be improved by using KBH₄ as a reducing agent, due to the electronic synergetic effect of Pt–Ni–B, and 96% for conversion of CMA and 88% for selectivity of HCMA are obtained over Pt–Ni/CNTs catalyst reduced by KBH₄. Furthermore, the hydrogenation rate of CMA and selectivity of CMA to HCMA over Pt–Ni/CNTs catalyst are significantly improved in the presence of trace base or acid promoters again. The best result (92% for conversion of CMA and 96% for selectivity of HCMA) is obtained when NaOAc is used as base promoter.     

Influence of Rare Earth (Ce, Sm, Nd, La, and Pr) on the Hydrogenation Properties of Chloronitrobenzene Over Pt/ZrO2 Catalyst

The effect of rare earths (Sm, Pr, Ce, Nd, and La) on the hydrogenation properties of chloronitrobenzene (CNB) over Pt/ZrO₂ catalyst was studied in ethanol at 303K and normal pressure. The results show that the hydrogenation of CNB can be carried out over Pt/ZrO₂ catalyst. The order of the hydrogenation rates of CNB is p>m>o, and the yield of chloroaniline (CAN) is p>o>m. The specific rate constant turnover frequency (TOF) expressed per surface Pt atom increases when the platinum catalyst is modified by rare earth. The conversion of CNB is >99% and CAN is the main product in the hydrogenation of CNB over PtM/ZrO₂ catalysts. The PtPr/ZrO₂ catalyst shows the best selectivity of CNB to CAN: 89.4mol% for o-CAN, 94.6mol% for m-CAN and 95.1mol% for p-CAN.     

Improvement of Pt/ZrO2 by CeO2 for high pressure CH4/CO2 reforming

CH₄/CO₂ reforming over Pt/ZrO₂, Pt/CeO₂ and Pt/ZrO₂ with CeO₂ was investigated at 2 MPa. Pt/ZrO₂, which shows stable activity under 0.1 MPa, and Pt/CeO₂ showed gradual deactivation with time at the high pressure. The deactivation was suppressed drastically on Pt/ZrO₂ with CeO₂ prepared by different impregnation order (co-impregnation of Pt and CeO₂ on ZrO₂, and consecutive impregnation of Pt and CeO₂ on ZrO₂). The amount of coke deposition was found insignificant and similar among all the catalysts (including Pt/ZrO₂ and Pt/CeO₂). Catalytic activity after the reaction for 24 h was in agreement with Pt particle size after the reaction for same period, indicating that the difference of the catalytic stability is mainly dependent on the extent of Pt aggregation through catalyst preparation, H₂ reduction, and the CH₄/CO₂ reforming. Pt aggregation and the amount of coke deposition were least pronounced on (Pt–Ce)/ZrO₂ prepared by impregnation of CeO₂ on Pt/ZrO₂ and the catalyst showed highest stability.     

Pt/Ni wet impregnated over Al incorporated mesoporous silicates: a highly efficient catalyst for anisole hydrodeoxygenation

This work reports, formation of benzene from anisole via hydrodeoxygenation process using vapour phase fixed bed reactor. The surface properties of bimetallic catalysts such as textural properties, acidic, and Pt/Ni dispersion has established by various characterization techniques. The reaction was carried out at 370 and 420 °C with space velocity 3.3 & 6.6 h^??1, over acidic and non-acidic supported mono and bimetallic catalysts. The optimum conversion and selectivity was observed at 420 °C and WHSV?=?3.3 h^??1 for all mono and bimetallic catalysts. Pt/Ni/Al-SBA-15 acidic bimetallic catalyst shows maximum anisole conversion 59% with benzene selectivity 37% under atmospheric pressure, due to the more acidic centres and high dispersion of Pt/Ni species on the bimetallic catalyst, enhance the anisole conversion; this was proved by NH₃-TPD and HR-TEM analysis. The acidic Pt/Ni bimetallic catalyst shows higher anisole conversion as compared to the mono metallic Pt/Ni catalysts and it works predominantly through demethylation and hydrogenolysis reaction pathway.     

Anion-modified zirconia: effect of metal promotion and hydrogen reduction on hydroisomerization of n-hexadecane and Fischer–Tropsch waxes

The effect of metal promoters on the activity and selectivity of tungstated zirconia (8 wt.% W) for n-hexadecane isomerization in a trickle bed continuous reactor is studied by using different metals (Pt, Ni, and Pd) and, in one case, by varying metal loading. Platinum is found to be the best promoter. The effect of hydrogen reduction is investigated using platinum-promoted tungstated zirconia catalysts (Pt/WO₃/ZrO₂, 0.5 wt.% Pt and 6.5 wt.% W). Pretreatment at temperatures between 300 and 400°C for 3 h in hydrogen is found to be slightly beneficial for achieving high yields of isohexadecane. A platinum promoted sulfated zirconia (Pt/SO₄/ZrO₂) is compared with a Pt/WO₃/ZrO₂ catalyst for the hydroisomerization of n-hexadecane in the same reactor at the same n-hexadecane conversion. The former is a good cracking catalyst and the latter is suitable for use as a hydroisomerization catalyst. In a 27-ml microautoclave reactor, studies of the hydroisomerization and hydrocracking of two Fischer–Tropsch (F–T) wax samples are carried out. Severe cracking can be effectively suppressed using a Pt/WO₃/ZrO₂ catalyst so as to obtain branched isomers in the diesel fuel or lube-base oil range.     

Role of Pt in the Activity and Stability of PtNi/CeO2–Al2O3 Catalysts in Ethanol Steam Reforming for H2 Production

Hydrogen production from ethanol reforming was investigated on bimetallic PtNi catalysts supported on CeO₂/Al₂O₃. Pt content was varied from 0.5 to 2.5 %. Physico-chemical characterization of the as-prepared and H₂-reduced catalysts by TPR, XRD and XPS showed that Pt phase interacted with the Ni and Ce species present at the surface of the catalysts. This interaction leads to an enhancement of the reducibility of both Ni and Ce species. Loadings of Pt higher than 1.0 wt% improved the activity and stability of the Ni/CeO₂–Al₂O₃ catalyst in ethanol steam reforming, in terms of lower formation of coke, C₂ secondary products and a constant production of CO₂ and H₂. The amount and type of carbon deposited on the catalyst was analyzed by TG–TPO while the changes in crystalline phases after reaction were studied by XRD. It was found that for Pt contents higher than 1 wt% in the catalysts, a better contact between Pt and Ce species is achieved. This Pt–Ce interaction facilitates the dispersion of small particles of Pt and thereby improves the reducibility of both Ce and Ni components at low temperatures. In this type of catalysts, the cooperative effect between Pt⁰, Ni⁰ and reduced Ce phases leads to an improvement in the stability of the catalysts: Ni provides activity in C–C bond breakage, Pt particles enhance the hydrogenation of coke precursors (C_xH_y) formed in the reaction, and Ce increases the availability of oxygen at the surface and thereby further enhances the gasification of carbon precursors.     

Effect of Catalyst Supports on Water‐Gas Shift Reaction at Ultrahigh Temperatures Using Syngas

Monometallic and bimetallic catalysts (Pt, Ni, and Pt‐Ni) with single support (Al₂O₃, TiO₂) and composite support (CeO₂/Al₂O₃, CeO₂/TiO₂) were prepared and tested for water‐gas shift reaction in a tubular quartz reactor. Syngas and steam with different steam‐to‐carbon ratios served as feedstock. The operating pressure was fixed while the reaction temperature was varied. The measured results indicated that the monometallic Ni/Al₂O₃ catalyst exhibits the lowest CO conversion and H₂ yield as compared with other catalysts. About the same CO conversion can be obtained from Pt and Pt‐Ni catalysts with single or composite support. However, higher H₂ yield can be achieved from the TiO₂‐supported catalyst compared with those supported by Al₂O₃. The experimental data also indicated that good thermal stability can be reached for the Pt‐based catalysts studied.     

Study of Ni and Pt catalysts supported on α-Al2O3 and ZrO2 applied in methane reforming with CO2

Ni and Pt catalysts supported on α-Al₂O_3, α-Al₂O₃-ZrO₂ and ZrO₂ were studied in the dry reforming of methane to produce synthesis gas. All catalytic systems presented well activity levels with TOF (s⁻¹) values between 1 and 3, being Ni based catalysts more active than Pt based catalysts. The selectivity measured at 650 °C, expressed by the molar ratio H₂/CO reached values near to 1. Concerning stability, Pt/ZrO₂, Pt/α-Al₂O₃-ZrO₂ and Ni/α-Al₂O₃-ZrO₂ systems clearly show lower deactivation levels than Ni/ZrO₂ and Ni or Pt catalysts supported on α-Al₂O₃. The lowest deactivation levels observed in Ni and Pt supported on α-Al₂O₃-ZrO₂, compared with Ni and Pt supported on α-Al₂O₃ can be explained by an inhibition of reactions leading to carbon deposition in systems having ZrO₂. These results suggest that ZrO₂ promotes the gasification of adsorbed intermediates, which are precursors of carbon formation and responsible for the main deactivation mechanism in dry reforming reaction.     

A novel sintering resistant and corrosion resistant Pt4ZrO2/C catalyst for high temperature PEMFCs

A novel Pt₄ZrO₂/C catalyst was prepared and compared with 20 wt.% Pt/C in terms of the sintering resistance and corrosion resistance. To evaluate their sintering resistance and corrosion resistance properties, an accelerated ageing test (AAT) was performed. The catalysts before and after AAT were characterized by cyclic voltammetry (CV), rotating disk electrode (RDE) and X-ray diffraction (XRD). After AAT, the dissolution rate of Pt and Zr in H₃PO₄ media (105 wt.%, 204 °C) was characterized by inductively coupled plasma-atomic emission spectroscopy (ICP-AES). The electrochemical area (ECA) changes of thin film electrodes based on Pt₄ZrO₂/C and Pt/C catalysts were also evaluated using continuous CV sweep technique. All the results showed that Pt₄ZrO₂/C has higher sintering resistance and corrosion resistance than Pt/C. ‘Anchor effect’ is proposed to explain the enhanced effect of ZrO₂ in Pt₄ZrO₂/C binary catalyst compared with Pt/C that contain platinum alone.     

On the contribution of X-ray absorption spectroscopy to explore structure and activity relations of Pt/ZrO2 catalysts for CO2/CH4 reforming

X-ray absorption spectroscopy (XAS) has proven to be a very useful technique in characterizing metal-based catalysts exposed to extreme operating conditions. The technique allows in situ evaluation of structural parameters (XAFS) and electronic properties (XANES). The elucidation of the nature and state of Pt-based catalysts in dry reforming of methane with carbon dioxide is presented as case study to show the contribution and potential of XAS to explore property/performance relationships for heterogeneous catalysts. Pt/ZrO₂ is an active and stable catalyst for the reaction between CH₄ and CO₂ to synthesis gas (H₂/CO). The activity and stability of the catalyst is strongly influenced by the catalyst pretreatment (calcination/reduction). The combination of hydrogen chemisorption, IR spectroscopy, XPS and XAS is shown to be suitable to track the changes of the state of the catalyst. In particular, it will be demonstrated, how XAFS helped to correctly attribute variations in the chemisorptive properties of Pt/ZrO₂ after severe temperature treatment to partial and reversible decoration of the small Pt particles with fragments of the oxide support. In situ tracking of the reduction of the catalysts by XANES additionally helped to semiquantitatively assess the partial reduction of the ZrO₂. Finally, XANES helped to demonstrate that CO₂ exposure under these severe conditions did not lead to detectable levels of surface oxidation of Pt. Based on XANES, IR spectroscopy and kinetic measurements it is concluded that in dry reforming activation of methane occurs on Pt, while CO₂ is activated on the support and the two entities react at the metal–support interface. This revised version was published online in June 2006 with corrections to the Cover Date.     

Electrocatalysis of oxygen reduction on carbon-supported PtCo catalysts prepared by water-in-oil micro-emulsion

Synthesis of carbon-supported PtCo/C using micro-emulsion method including simultaneous procedure and sequential procedures in both acid and alkaline media was reported. UV-vis and electron microscopy were used to characterize the formation, surface morphology and distribution of PtCo nanoparticles. Crystallite structure of catalysts was analyzed from XRD patterns. Catalytic properties of PtCo/C catalysts synthesized were compared with commercial Pt/C using RDE based on both mass activity (MA) and specific activity (SA). PtCo/C catalysts prepared in both acidic and basic conditions showed better performance than commercial Pt/C catalyst. High-temperature heat treatment was found useful only to PtCo/C by sequential procedure. The peroxide yield was also explored using RRDE technique. The H₂O₂ yield results were correlated with SA and R values (ratio of charge transferred about Co and Pt on the surface of catalyst) obtained from CVs in 1 M KOH solution. A sacrificial Co oxidized effect on impediment of adsorption of OH may cause higher catalytic properties and higher H₂O₂ yield to Pt base alloy catalysts.     

Effective combination of non-thermal plasma and catalyst for removal of volatile organic compounds and NOx

A plasma/catalyst hybrid reactor was designed to overcome the limits of plasma and catalyst technologies. A two-plasma/catalyst hybrid system was used to decompose VOCs (toluene) and NOx at temperature lower than 150 °C. The single-stage type (Plasma-driven catalyst process) is the system in which catalysts are installed in a non-thermal plasma reactor. And the two-stage type (Plasma-enhanced process) is the system in which a plasma and a catalyst reactor are connected in series. The catalysts prepared in this experiment were Pt/TiO₂ and Pt/Al₂O₃ of powder type and Pd/ZrO₂, Pt/ZrO₂ and Pt/Al₂O₃ which were catalysts of honeycomb type. When a plasma-driven catalyst reactor with Pt/Al₂O₃ decomposed only toluene, it removed just more 20% than the only plasma reactor but the selectivity of CO₂ was remarkably elevated as compared with only the plasma reactor. In case of decomposing VOCs (toluene) and NOx using plasma-enhanced catalyst reactor with Pt/ZrO₂ or Pt/Al₂O₃, the conversion of toluene to CO₂ was nearly 100% and about 80% of NOx was removed. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

The Oxidation of Methane at Low Temperatures Over Zirconia-Supported Pd,Ir and Pt Catalysts and Deactivation by Sulfur Poisoning

Abstract  

The oxidation of methane over zirconia-supported Pd, Ir, and Pt catalysts at low temperatures under an oxidizing atmosphere and the effect of SO₂ on this reaction were investigated. An Ir–Pt/ZrO₂ catalyst exhibited high activity and low deactivation by SO₂. Characterization of the catalyst indicated the presence of a highly oxidized Pt species that was stabilized by the addition of Ir.     

Activity,selectivity, and methanol tolerance of novel carbon-supported Pt and Pt<Subscript>3</Subscript>Me (Me = Ni,Co) cathode catalysts

The activity, selectivity, and methanol tolerance of novel, carbon supported high-metal loading (40 wt.%) Pt/C and Pt₃Me/C (Me = Ni, Co) catalysts for the O₂ reduction reaction (ORR) were evaluated in model studies under defined mass transport and diffusion conditions, by rotating (ring) disk and by differential electrochemical mass spectrometry. The catalysts were synthesized by the organometallic route, via deposition of pre-formed Pt and Pt₃Me pre-cursors followed by their decomposition into metal nanoparticles. Characteristic properties such as particle sizes, particle composition and phase formation, and active surface area, were determined by transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and X-ray diffraction. For comparison, commercial Pt/C catalysts (20 and 40 wt.%, E-Tek, Somerset, NJ, USA) were investigated as well, allowing to evaluate Pt loading effects and, by comparison with the pre-cursor-based catalyst with their much smaller particle sizes (1.7 nm diameter), also particle size effects. Kinetic parameters for the ORR were evaluated; the ORR activities of the bimetallic catalysts and of the synthesized Pt/C catalyst were comparable and similar to that of the high-loading commercial Pt/C catalyst; at typical cathode operation potentials H₂O₂ formation is negligible for the synthesized catalysts. Due to their lower methanol oxidation activity the bimetallic catalysts show an improved methanol tolerance compared to the commercial Pt/C catalysts. The results indicate that the use of very small particle sizes is a possible way to achieve reasonably good ORR activities at an improved methanol tolerance at DMFC cathode relevant conditions.     

Bulk oxygen promoted water–gas shift reaction activity over Pt/Ce0.6Zr0.4O2 catalyst

The water–gas shift (WGS) reaction of Pt/Ce_0.6Zr_0.4O₂ catalyst was studied, as well as the reference catalysts Pt/CeO₂ and Pt/ZrO₂. In situ electronic conductivity measurements under reactive atmosphere show that surface oxygen vacancies of Pt/Ce_0.6Zr_0.4O₂ diffuse into the bulk materials at the temperature typical for the operation of WGS reaction, i.e., bellow 623 K. Compared with Pt/CeO₂, it was found that the oxygen storage capacity (OSC) was higher for Pt/Ce_0.6Zr_0.4O₂ catalyst. Pt/Ce_0.6Zr_0.4O₂ shows a markedly higher CO conversion rate than Pt/CeO₂ and Pt/ZrO₂ catalysts, which was interpreted by more active oxygen species available and higher coke resistance.     

A new route for the electrodeposition of platinum-nickel alloy nanoparticles on multi-walled carbon nanotubes

An electrochemical method was developed to deposit platinum (Pt) and nickel (Ni) nanoparticles on multi-walled carbon nanotubes (MWCNTs) through a three-step process. X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDX) show the alloy formation for Pt and Ni with a ratio of 1:1. The presence of Pt(0), Ni(0), Ni(OH)₂, NiOOH and slight NiO was deduced from XPS data. Electrocatalytic properties of the resulting PtNi/MWCNT electrode for methanol oxidation reaction were investigated. Compared with Pt/MWCNT, an appreciably improved resistance to CO poisoning was observed for the PtNi/MWCNT electrode, which was interpreted by a mechanism based on the bifunctional catalysis. The successful preparation of PtNi/MWCNT nanocomposites opens a new path for an efficient dispersion of the promising electrocatalysts in the direct methanol fuel cells.     

Modulating morphology and textural properties of ZrO2 for supported Ni catalysts toward dry reforming of methane

This work presents a facile and efficient approach to modulate morphology and textural properties of ZrO₂ through ammonium fluoride‐urea assisted hydrothermal (FUAH) method with diverse parameters including molar ratio of NH₄F to zirconium (n_f/z), molar ratio of urea to zirconium (n_u/z), hydrothermal temperature (T_hydroth), and hydrothermal time (t_hydroth), which serve as support for supported Ni catalysts toward dry reforming of methane (DRM) to produce synthesis gas. The plausible mechanism for forming ZrO₂ supports with different morphologies under diverse hydrothermal conditions was proposed. Various characterization techniques were employed to investigate the effect of preparation parameters on the morphology and textural properties of the as‐synthesized ZrO₂ supports, as well as to reveal the structure‐performance relationship of the Ni/ZrO₂ catalysts prepared by L‐arginine assisted incipient wetness impregnation method toward DRM reaction. The developed supported Ni catalyst on hierarchically structured ZrO₂ with pinecone shape prepared by FUAH method (Ni/ZrO₂‐FUAH) demonstrates higher activity and stability for DRM than that on ZrO₂ prepared by traditional hydrothermal method (Ni/ZrO₂‐H). The higher activity of Ni/ZrO₂‐FUAH than Ni/ZrO₂‐H can be ascribed to the higher Ni dispersion, smaller Ni crystalline size, and enhanced reducibility of NiO, significantly affected by morphology of support, as well as the higher coke‐resistance catalytic stability can be ascribed to smaller Ni particle size and stronger Ni‐support interaction, strongly dependent on morphology and textural properties of ZrO₂ supports that affected by FUAH process parameters. The outstanding catalytic performance of the developed Ni/ZrO₂‐FUAH catalyst allows it to be a promising candidate for synthesis gas production through DRM reaction. © 2017 American Institute of Chemical Engineers AIChE J, 63: 2900–2915, 2017     

Carbon dioxide reforming of methane over Co-X/ZrO2 catalysts (X = La,Ce, Mn,Mg, K)

Dry reforming of methane has been studied over Co/ZrO₂ catalysts promoted with different metal additives (La, Ce, Mn, Mg, K) aiming to improve the performance of the catalysts and increase their resistance to coking. Scanning electron microscopy studies and different activity levels of the catalysts clearly show that the type of the promoter significantly affected the metal dispersion properties and catalytic performances of Co/ZrO₂ catalysts. La-modified catalyst exhibited high stability, but moderate activity. It showed no severe coke deposition. Ce-doped Co/ZrO₂ displayed the highest activity among all the catalysts prepared and had a very limited activity loss.     

Constructing synergy of sufficient hydroxyl and oxygen in PtNi/Al2O3 enables room-temperature catalytic HCHO oxidation

Rational engineering of noble metal/transition metal bimetallic catalysts is considered as an effective way to constructing synergistic effect between adsorbed oxygen and hydroxyl for enhanced catalytic formaldehyde oxidation. Herein, we developed a Pt–Ni bimetallic catalysts loading on γ-Al₂O₃ support for room-temperature formaldehyde oxidation. Catalytic experiment results showed that the conversion rate was >97% with a >100 h stability. Several noble metals (Pd, Au, and Ag) were compared to identify the activity effect in formaldehyde oxidation. The activity and stability test in different atmospheres and in situ infrared test suggested that the PtNi/γ-Al₂O₃ has the best activity and stability. At a meantime, the results also demonstrated that Pt sites motivate more surface adsorbed oxygen through activating ambient oxygen molecules, while the neighboring Ni atoms contribute to adsorbed hydroxyl, thereby offering sustainable activity. The high efficiency and stability of PtNi/γ-Al₂O₃ catalysts for formaldehyde oxidation could be a promising candidate for air purification.     

Highly Active and Selective Nickel–Platinum Catalyst for the Low Temperature Hydrogenation of Maleic Anhydride to Succinic Anhydride and Synthesis of Succinic Acid at 40 °C

Abstract  

PtNi bimetallic and Ni monometallic catalysts supported on HY–Al₂O₃, HX–Al₂O₃, ZSM-5–Al₂O₃, USY–Al₂O₃, Beta–Al₂O₃ and Al₂O₃ were prepared and evaluated for the hydrogenation of maleic anhydride in the temperature range of 40–150 °C. Results from flow reactor studies showed that supports strongly affected the catalytic properties of different bimetallic and monometallic catalysts. The results showed that the HY–Al₂O₃ support exhibited the highest activity and selectivity. Using NiPt/Al₂O₃–HY catalyst and performing the reaction, it was possible to carry out the lowest reaction temperature ever carried at 100% conversion. Adding a small amount of Pt (0.5) to the Ni (5%)/Al₂O₃–HY catalyst that is effective for increasing the selectivity and activity. We also found that PtNi is an efficient catalyst for the one-pot conversion of maleic acid into succinic acid with 100% conversion at 40 °C.