Coke-resistance over Rh–Ni bimetallic catalyst for low temperature dry reforming of methane

Methane and carbon dioxide can be converted into syngas using the prospective dry reforming of methane technology. Carbon deposition is a major cause of catalyst deactivation in this reaction, especially at low temperature. The superior stability of bimetallic catalysts has made their development more and more appealing. Herein, a series of bimetallic RhNi supported on MgAl₂O₄ catalysts were synthesized and used for low temperature biogas dry reforming. The results demonstrate that the bimetallic RhNi catalyst can convert CH₄ and CO₂ by up to 43% and 52% over at low reaction temperature (600 °C). Moreover, the reaction rate of CH₄ and CO₂ of RhNi–MgAl₂O₄ remains stable during the 20 h long time stability test, most importantly, there was no obviously carbon deposition observed over the spent catalyst. The enhanced coking resistance should be attributed to the addition of a little amount of noble metal Rh can efficiently suppress dissociation of CH_X1 species into carbon, and the high surface areas of MgAl₂O₄ support can also promote the adsorption and activation of carbon dioxide to generate more O1 species. Balancing the rate of methane dissociation and carbon dioxide activation to inhibit the development of carbon deposition is a good strategy, which provides a guidance for design other high performance dry reforming of methane catalysts.     

Non-noble Ni–Cu/ACC bimetallic catalyst for dehydrogenation of liquid organic hydrides for hydrogen storage

The effect of Cu on dehydrogenation activity of Ni has been observed when dehydrogenation of methyl cyclohexane (MCH) was carried out by using bimetallic Ni–Cu supported on activated carbon cloth (ACC) catalysts with various Ni to Cu ratios and constant total metal content of about 10 wt%. The dehydrogenation of MCH was studied for delivery of clean hydrogen to hydrogen fueling station. Catalysts have been synthesized by adsorption method and characterized by atomic absorption spectroscopy (AAS), X-ray powder diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Among all combinations of this study 8 wt% Ni + 2 wt% Cu/ACC was found to show strong synergetic effect. This catalyst exhibited relatively high H₂ evolution rate 39.4 mmol/g_met/min during the dehydrogenation of MCH. At the same time methane evolution rate was relatively low which indicated insignificant side reaction of hydrogenolysis. The study reveals that presence of specific amount of Cu enhances the dehydrogenation activity of Ni and suppresses the hydrogenolysis activity for the same. The Ni–Cu/ACC catalyst may be a potential non-noble metal catalyst for dehydrogenation reaction.     

Catalytic steam reforming of glycerol over Ni–La2O3–CeO2/SBA-15 catalyst for stable hydrogen-rich gas production

Ni-based catalysts (Ni, Ni–La₂O₃, and Ni–La₂O₃–CeO₂) on mesoporous silica supports (SBA-15 and KIT-6) were prepared by an incipient wetness impregnation and tested in glycerol steam reforming (GSR) for hydrogen-rich gas production. The catalysts were characterized by the N₂-physisorption, TPD, X-ray diffraction (XRD), SEM-EDS, and TEM techniques. N₂-physisorption results of calcined catalysts highlight that adding of La₂O₃ increased surface area of the catalyst by preventing pore mouth plugging in SBA-15, which was frequently observed due to the growth of NiO crystals. A set of GSR experiments over the catalysts were performed in an up-flow continuous packed-bed reactor at 650 °C and atmospheric pressure. The highest hydrogen concentration of 62 mol% was observed with a 10%Ni–5%La₂O₃ –5%CeO₂/SBA-15 catalyst at a LHSV of 5.8 h⁻¹. Adding of CeO₂ to the catalyst appeared to increase catalytic stability by facilitating the oxidative gasification of carbon formed on/near nickel active sites of Ni–La₂O₃–CeO₂/SBA-15 and Ni–La₂O₃–CeO₂/KIT-6 catalyst during the glycerol steam reforming reaction.     

The study of bimetallic Ni–Co/cordierite catalyst for cracking of tar from biomass pyrolysis

In order to crack the tar from biomass pyrolysis, five cordierite-supported monolithic catalysts with different Ni/Co ratio were prepared by vacuum wetness impregnation. All catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction (TPR), Brunauer–Emmett–Teller (BET), and scanning electron microscope (SEM). XRD and XPS characterization results show the inexistence of spinel structure such as NiAl₂O₄ and CoAl₂O₄. TPR characterization results suggest the possible formation of Ni–Co alloy. BET characterization results show that the effect of Ni/Co ratio on catalyst specific surface area is obvious. The catalytic test results show that the performance of bimetallic catalyst is better than that of monometallic catalyst. The Ni₃Co₁/cordierite catalyst exhibits the best catalytic performance among all bimetallic catalysts, its tar conversion and gas yield reach 96.4% and 1.21 Nm³/kg, respectively, at a weight hourly space velocity (WHSV) of 1.4 h⁻¹.     

In-situ hydrodeoxygenation of phenol by supported Ni catalyst – explanation for catalyst performance

In-situ hydrodeoxygenation of phenol with aqueous hydrogen donor over supported Ni catalyst was investigated. The supported Ni catalysts exerted very poor performance, if formic acid was used as the hydrogen donor. Catalyst modification by loading K, Na, Mg or La salt could not make the catalyst performance improved. If gaseous hydrogen was used as the hydrogen source the activity of Ni/Al₂O₃ was pretty high. CO₂ was found poisonous to the catalysis, due to the competitive adoption of phenol with CO₂. If formic acid was replaced by methanol, the catalyst performance improved remarkably, with major products of cyclohexanone and cyclohexanol. The better effect of methanol enlightened the application of the supported Ni catalyst in in-situ hydrodeoxygenation of phenol.     

Anti-sintering mesoporous Ni–Pd bimetallic catalysts for hydrogen production via dry reforming of methane

In this work, a series of mesoporous silica supported nickel or nickel-palladium catalysts were synthesized and performed in dry reforming of methane (DRM) reaction for producing syngas. Compared with the monometallic catalyst, the Ni–Pd bimetallic catalysts, especially synthesized by the OA-assisted route, exhibited promising yields of H₂ and CO in the catalytic DRM reaction, achieved at 63% and 69% over NiPd-SP-OA bimetallic catalyst at the reaction temperature of 700 °C, respectively. TEM image results confirmed that no obvious sintering phenomenon happened on spent NiPd-SP-OA bimetallic catalyst within 1550 min time-on-stream reaction. Based on the results of XRD, XPS and H₂-TPR, it could be known that the superior catalytic performance on NiPd-SP-OA catalyst were main ascribed to the smaller-sized Ni nanoparticles with a uniform metal dispersion and a larger fraction of exposed active sites (Ni⁰).     

Biogas reforming for hydrogen production over a Ni–Co bimetallic catalyst: Effect of operating conditions

A Ni–Co bimetallic catalyst, Ni–Co/La₂O₃/Al₂O₃, was prepared by conventional incipient wetness impregnation. It shows a high level of activity and excellent stability for biogas reforming. This work examines how operating conditions, such as the reaction temperature, operating pressure, feed ratio, gas hourly space velocity (GHSV), and CO₂ excessive coefficient, affect the catalytic performances of the catalyst. The experimental biogas is simulated with CH₄ and CO₂ at a molar ratio of 1, without any dilute gas. The catalyst was also characterized by XRD, BET, TEM and TG-DSC. In a stability test of 510 h under the conditions of 800 °C, 1 atm, and a GHSV of 6000 ml g_cat⁻¹ h⁻¹, the average coking rate over the catalyst was only about 0.0374 mg g_cat⁻¹ h⁻¹. The experimental results also indicate that the dynamic equilibrium between the deposition and gasification of carbon deposited on the surface of the catalyst can be established during the reaction. The aggregation of metallic Ni/Co and the formation of filamentous carbon over the surface of the catalyst can be inhibited effectively. During the last 50 h of the 510 h stability test, the average conversion of CH₄ and CO₂, the selectivity to H₂ and CO, and ratio of H₂/CO were 95.2%, 96.7%, 95.0%, 98.3%, and 0.96, respectively.     

Catalytic performance of Ni–Al nanoparticles fabricated by arc plasma evaporation for methanol decomposition

The catalytic properties of Ni-25 at% Al (Ni25Al) nanoparticles fabricated by arc plasma evaporation toward methanol decomposition were studied at temperatures ranging from 513 to 753 K. The Ni25Al nanoparticles showed much higher activity than gas atomized Ni25Al powders. They showed a high degree of selectivity for methanol decomposition into H₂ and CO. Side reactions such as methanation and water-gas shift reaction were suppressed to a high temperature of 673 K, which is hardly achieved for common Ni catalysts. Detailed characterization of the Ni25Al nanoparticles showed that they were composed of Ni, Ni₃Al, and Al₂O₃ phases with Ni and Al oxides on the surface of the Ni and Ni₃Al phases. The Ni oxides were reduced to Ni phase by a hydrogen reduction prior to methanol decomposition, while the Al oxides remained unchanged. It is supposed that the Ni phase provided the active sites for methanol decomposition, and the Ni₃Al and Al₂O₃ phases acted as supports for the Ni phase. Probably the Ni₃Al and Al₂O₃ phases provided good resistance to agglomeration of the Ni phase during the reaction, which might contribute to maintain the high catalytic performance of the nanoparticles for methanol decomposition.     

Influence of Pd addition on the electrochemical performance of Mg–Ni–Ti–Al-based metal hydride for Ni–MH batteries

Amorphous Mg_0.9Ti_0.1NiAl_0.05 and Mg_0.9Ti_0.1NiAl_0.05Pd_0.1 alloys were prepared by high energy ball milling and evaluated as metal hydride electrodes for Ni–MH batteries. The Mg_0.9Ti_0.1NiAl_0.05Pd_0.1 alloy showed a much higher cycle life with a capacity retention of 72% after 100 cycles (C_100th = 288 mAh g⁻¹) compared to 26% for the Pd-free alloy (C_100th = 117 mAh g⁻¹). This was mainly attributed to the improvement of the alloy oxidation resistance in KOH electrolyte with Pd addition, as confirmed by cyclic voltammetry experiments and X-ray diffraction analyses on cycled electrodes. In addition, in situ acoustic emission (AE) measurements revealed that the energy of the AE signals related to the particle cracking is lower for the Mg_0.9Ti_0.1NiAl_0.05Pd_0.1 electrode, suggesting that the cracks are smaller in size than with the Pd-free alloy. The Mg_0.9Ti_0.1NiAl_0.05Pd_0.1 electrode also displayed a higher discharge rate capability than the Mg_0.9Ti_0.1NiAl_0.05 electrode. On the basis of their respective electrochemical pressure–composition isotherm, it was shown that the presence of Pd in the alloy decreases the thermodynamic stability of the metal hydride. Through a comparative analysis of discharge polarization curves, it was also shown that Pd addition decreases substantially the H-diffusion resistance in the alloy whereas its positive effect on the charge-transfer resistance is limited.     

Hydrogen generation from liquid reforming of glycerin over Ni–Co bimetallic catalyst

Glycerin is a low cost renewable byproduct of the biodiesel industry, and can be reformed into hydrogen. Here we describe the development of cerium promoted nickel cobalt catalysts on alumina supports for the liquid phase reforming of aqueous glycerine in subcritical water. The bimetallic Ni–Co catalyst was prepared using the urea matrix combustion method over a wide range of compositions both with and without cerium. TPR profiles indicated a synergism between the metals, however, the catalysts deactivated due to carbon deposition as plaques, and in some compositions due to sintering. Cerium (2Ce–Ni₁Co₃) suppressed sintering and lowered methane selectivity by comparison with Ni₁Co₃ alone.     

Co–Ni alloy supported on CeO2 as a bimetallic catalyst for dry reforming of methane

Dry reforming of methane (DRM) is an effective route to convert two major greenhouse gas (CH₄ and CO₂) to syngas (H₂ and CO). Herein, in this work, monometallic Ni/CeO₂ and a series of bimetallic Co–Ni/CeO₂ catalysts with Co/Ni ratios between 0 and 1.0 have been tested for DRM process at 600–850 °C, atmospheric pressure and a CH₄/CO₂ ratio of 1. The catalysts were characterized by X-ray diffraction, hydrogen-temperature programmed reduction, CO₂-Temperature programmed desorption, X-ray photoelectron spectroscopy, and thermogravimetric analysis. The catalyst with a Co/Ni ratio of 0.8 (labeled as 0.8 Co–Ni/CeO₂) exhibited the highest catalytic activity (CH₄ and CO₂ initial conversion for 80% and 85% at 800 °C, respectively) and the highest stability (less carbon deposition after 600min). This improved activity can be attributed to the Co–Ni alloy, which formed after reduction. Its weak chemisorption with hydrogen results in inhibition of reverse water gas shift reaction. In addition, Co-promoted the adsorption of surface oxygen enhances carbon removal, making it more stable.     

Catalytic performance and kinetic modeling of ethylene glycol steam reforming over surfactant-modified Pd–Ni/KIT-6

In the current study, steam reforming of ethylene glycol as a well-known bio-oxygenate, was carried out over 2%Pd–10%Ni/KIT-6 catalyst in a fixed-bed reactor. 2%Pd–10%Ni/KIT-6 was synthesized via surfactant-assisted impregnation method, whose physicochemical properties were determined by XRD, XRF, BET, FE-SEM, EDX-dot mapping, TEM, H₂-TPR, NH₃-TPD and TGA analyses. The performance of the synthesized catalyst was investigated at temperatures from 623 to 773 K and at 10 wt% of ethylene glycol in water. Furthermore, the W_cat/F_EG0 ratio varied between 100.08 and 202.22 (g h mol^?1). At T = 773 K and W_cat/F_EG0 = 202.22, ethylene glycol conversion and H₂ yield were 99.8% and 71.36%, respectively. Also, a stability test of 2%Pd–10%Ni/KIT-6 was conducted for 28 h. No significant change was shown in the catalytic activity. Some different models were used to describe the kinetic behavior. The power-law model indicated that the reaction order changed with temperature. The kinetic data were interpreted by the Langmuir-Hinshelwood models, in which the surface reaction between the adsorbed reactants was considered as a rate-determining step. The activation energy for the Langmuir-Hinshelwood and power-law models were 28.03 and 33.07 kJ mol^?1, respectively. This synthesized nanocatalyst as the first Pd–Ni/zeolite in SREG through well-known kinetics and mechanism, is superior in high stability, excellent EG conversion, good yield and selectivity to H₂ and less production of toxic products.     

Reliability of hydrogen sensing based on bimetallic Ni–Pd/graphene composites

Graphene-supported nickel–palladium (Ni–Pd) bimetallic nanoparticles (Ni–Pd/Gr) were synthesized using a simple chemical method, followed by a post-thermal annealing process. The characteristics of resistivity-type hydrogen (H₂) sensors composed of Pd–Gr composites (with small amounts of Ni added to the Pd nanoparticles (Pd NPs)) were investigated in detail. Pd NPs with various amounts of Ni embedded into the Pd lattice were synthesized by varying the molar ratios of the Ni/Pd precursors. The results from this work indicate that the addition of Ni not only enhances performance, but also reduces the hysteresis behavior of the Pd–Gr composite based H₂ sensors. H₂ was detectable from 1 to 1000 ppm based on a rapid recovery response with suitable Ni/Pd percentages. At the optimal Ni/Pd percentage of 7% (Ni/Pd ∼7%), sensors showed a small enhancement of sensitivity, fast recovery, and minimum hysteresis effect. From our experiment, the addition of Ni to Pd NPs results in a reduction of the hysteresis effect and reliability on H₂ sensors based on Pd–Gr composites.     

Ammonia decomposition over SiO2-supported Ni–Co bimetallic catalyst for COx-free hydrogen generation

NH₃ decomposition over non-noble catalyst to generate CO_x-free H₂ has attracted great attention in recent years. In this work, fumed SiO₂-supported Ni, Co and Ni–Co bimetallic catalysts are synthesized by using a co-impregnation method and evaluated for NH₃ decomposition, which shows that the bimetallic catalysts exhibit better catalytic activity than the monometallic ones. This enhanced activity observed on bimetallic catalyst can be largely attributed to the more appropriate catalyst metal-N binding energy resulting from the synergistic effect between Ni and Co in the formed Ni–Co alloy. Among the synthesized catalysts, Ni₅Co₅/SiO₂ synthesized with the Ni/Co molar ratio of 5:5 achieves 76.8% NH₃ conversion under a GHSV of 30,000 mL h⁻¹ g⁻¹_cat at 550 °C and shows the best catalytic activity, which can be further improved by doping with K (78.1% NH₃ conversion at 30,000 mL h⁻¹ g⁻¹_cat), and the obtained Ni₅Co₅/SiO₂–K also shows excellent catalytic stability.     

Synthesis and electrocatalytic alcohol oxidation performance of Pd–Co bimetallic nanoparticles supported on graphene

Magnetic Pd–Co bimetallic nanoparticles supported on reduced graphene oxide sheets (Pd–Co/RGO) with excellent electrocatalytic performance have been synthesized by a rapid reducing method, using sodium hypophosphite as the reducing agent. The loading and crystalline phase of cobalt in the Pd–Co/RGO hybrids varied as to the initial amount of cobalt salt and reducing agent. Transmission electron microscopy images show that the mean size of the Pd–Co bimetallic nanoparticles was about 10–13 nm and without significant agglomeration. At the same Pd loading on graphene, the current densities of the forward anodic peak of the different Pd–Co/RGO catalysts was decreased by about 25% when compared with that of the pure Pd nanoparticles supported on reduced graphene oxide for both methanol and ethanol oxidation. However, chronoamperometry tests confirmed that the stability was increased by up to 240% and 225% for methanol oxidation and ethanol oxidation, respectively. It is hypothesized that the Co layer on Pd partially blocks Pd sites sacrificing a small portion of the activity of the catalysts, but it leaves the remaining Pd more active and thus enhances alcohol oxidation kinetics and tolerance to poisoning intermediates. Catalytic performance of the Pd–Co/RGO hybrids for alcohol oxidation is primarily affected by the interaction among Pd, Co, and graphene.     

Improved hydrogen gas sensing performance of Pd–Ni alloy thin films

This study examined the palladium (Pd)-nickel (Ni) alloy films' ability to detect hydrogen (H₂) at various Ni concentrations. The co-sputtering method was used to make the Pd–Ni alloy sensors. The response of the Pd–Ni alloys sensor reduced linearly as Ni_8% concentration was added to Pd, and the resistance of the Pd–Ni alloys was reversible upon exposure to H₂ gas with absorption and desorption characteristics. The experimental findings demonstrated that the Pd–Ni alloy sensor response time of 11 s was much faster than that of pure Pd, with great selectivity and stability for a period of 90 days.     

Highly-dispersed surfactant-free bimetallic Ni–Pt nanoparticles as high-performance catalyst for hydrogen generation from hydrous hydrazine

Highly-dispersed surfactant-free bimetallic Ni–Pt nanoparticles (NPs) with a particle size as small as 2.4 nm were successfully synthesized using NaBH₄ as reducing agent in the presence of NaOH, which exhibit excellent catalytic performance with very fast kinetics for selective decomposition of hydrous hydrazine to hydrogen at room temperature. NaOH plays an important role in the formation of highly-dispersed Ni–Pt nanoparticles. The present results bring light to new opportunities in the development of high-performance metal nanoparticle catalysts and encourage the effective application of hydrous hydrazine as a promising hydrogen storage material.     

Top-down preparation of Ni–Pd–P@graphitic carbon core-shell nanostructure as a non-Pt catalyst for enhanced electrocatalytic reactions

Electrochemical reactions such as the oxygen evolution reaction (OER), oxygen reduction reaction (ORR), and methanol oxidation reaction (MOR) are essential for energy conversion applications such as water electrolysis and fuel cells. Furthermore, Pt or Ir-related materials have been extensively utilized as electrocatalysts for the OER, ORR, and MOR. To reduce the utilization of precious metals, innovative catalyst structures should be proposed. Herein, we report a bi-metallic phosphide (Ni₂P and PdP₂) structure surrounded by graphitic carbon (Ni–Pd–P/C) with an enhanced electrochemical activity as compared to conventional electrocatalysts. Despite the low Pd content of 3 at%, Ni–Pd–P/C exhibits a low overpotential of 330 mV at 10 mA cm^?2 in the OER, high specific activity (2.82 mA cm^?2 at 0.8 V) for the ORR, and a high current density of 1.101 A mg^?1 for the MOR. The superior electrochemical performance of Ni–Pd–P/C may be attributed to the synergistic effect of the bi-metallic phosphide structure and core-shell structure formed by graphitic carbon.     

Study on the role of Pt and Pd in Pt–Pd/TiO2 bimetallic catalyst for H2 oxidation at room temperature

The hydrogen safety issue is spotlighted as the hydrogen process is extended. For this reason, we studied catalysts for H₂ oxidation at room temperature to ensure hydrogen safety. Catalysts were prepared by different preparation methods and compared to evaluate the role of Pt and Pd in Pt–Pd/TiO₂ catalysts. The catalytic activity was significantly enhanced when activity metal size was small and it was exposed to catalyst surface to a high Pd ratio. For the 0.1%Pt-0.9%Pd/TiO₂ catalyst, high hydrogen conversion of 90% was obtained under the condition of 0.5% hydrogen injection. To understand the correlation between activity and characteristics of catalyst, the physicochemical characteristics of the various catalysts were investigated by X-ray photoelectron spectroscopy (XPS), temperature-programmed oxidation and reduction (TPOR) and Field Emission-Transmission Electron Microscope (FE-TEM) analysis. From these analysis, it was found that Pt served the role of highly dispersion of active metal (Pt–Pd) and as with increasing Pd ratio of active metal, hydrogen activity was increased, which indicates that hydrogen oxidation had proceeded on the Pd site. Finally, the valence state of the Pd influenced hydrogen oxidation activity of Pt–Pd/TiO₂, which increased with increasing ratio of Pd⁰/Pd_Total.     

Catalytic performance of Samarium-modified Ni catalysts over Al2O3–CaO support for dry reforming of methane

Mesoporous calcina-modified alumina (Al₂O₃–CaO) support was produced through the simple and economical co-precipitation method, then nickel (Ni, 10 wt%) and samarium (Sm, 3 wt%) ions loaded by two-solvent impregnation and one-pot strategies. The unpromoted/samarium-promoted catalysts were evaluated using X-ray Diffraction (XRD), High-Resolution Transmission Electron Microscopy (HR-TEM), nitrogen adsorption-desorption, Temperature Programmed Oxidation/Reduction (TPR/TPO), and Field Emission Electron Scanning Microscopy (FE-SEM) methods, then investigated in methane dry reforming. The results revealed that with adding samarium to Ni catalyst through impregnation method, the average Ni crystallite size and specific surface area decreased from 11.5 to 5.75 nm and from 76.08 to 30.9 m²/g, respectively; as a result, the catalytic activity increased from about 50% to 68% at 700 °C. Furthermore, the TPO and FE-SEM tests indicated the formation of carbon with nanotube nature on the catalyst surface.