Nano-Pd/CeO2 catalysts for hydrogen storage by reversible benzene hydrogenation/dehydrogenation reactions

Nano-CeO₂ supports, which have different structure from different preparation methods, were used to prepare nano-Pd/CeO₂ catalysts. The hydrogen storage capacity of prepared nano-Pd/CeO₂ catalysts were studied via vapor phase benzene hydrogenation and cyclohexane dehydrogenation reactions. Results show that the prepared Pd/CeO₂ catalysts exhibit excellent benzene hydrogenation and cyclohexane dehydrogenation performances. The catalytic performance of the Pd/CeO₂ catalysts is related to the dispersion of metallic Pd, hydrogen adsorption-desorption ability and structure of Pd/CeO₂ catalysts and so on. And those properties are also directly affected by the morphology and mesoporous structure of the prepared nano-Pd/CeO₂ catalysts that can be regulated by CeO₂ support preparation methods. The synergistic effect between metal Pd, CeO₂ support and their structures can effectively promote benzene hydrogenation and cyclohexane dehydrogenation, thus promoting hydrogen storage capacity. The prepared Pd/CeO₂-HT catalyst, which has high specific surface area, developed pore structure and highly dispersed metal Pd species, exhibits superior catalytic performances. And, the Pd/CeO₂-HT catalyst exhibits superior catalytic hydrogen storage performances. The benzene conversion over it at 200 °C reaches 99.5%. Whereas the cyclohexane conversion at 450 °C is 65.3%, and the H₂ production capacity is 73.77 g/h.     

Hydrogen production by steam reforming of ethanol over Co/CeO2 catalysts: Effect of cobalt content

The Co/CeO₂ catalysts obtained by co-precipitation method were used in the steam reforming of ethanol (SRE). The influence of cobalt active phase content (15–29 wt%), the reaction temperature (420–600 °C) and H₂O/EtOH molar ratio (12/1 and 6/1) were examined. The physicochemical characterization revealed that the cobalt content of the catalyst influences the metal-support interaction which results in catalyst performance in SRE process. The differences between catalytic properties of the Co/CeO₂ catalysts with different metal loading in SRE process decayed at 500 °C for H₂O/EtOH = 12/1. The best performance among the tested catalysts showed the 29Co/CeO₂ catalyst with the highest cobalt content, exhibiting the highest ethanol conversion, selectivity to two most desirable products and the lowest selectivity to by-products in comparison with catalysts containing smaller amount of metal. Its catalytic properties results probably from its unique physicochemical properties, i.e this catalyst contains large amount of cobalt but the metal crystallites are relatively small. Regardless cobalt content, an increase in the water-to-ethanol molar ratio in the feed increased the concentration of hydrogen an carbon dioxide and decreased formation of carbon monoxide, acetone, aldehyde and ethylene.     

OER properties of Ni–Co–CeO2/Ni composite electrode prepared by magnetically induced jet electrodeposition

Hydrogen production from water electrolysis with catalysts is a simple, effective, and environmentally friendly way. However, the slow kinetics of the oxygen evolution reaction (OER) directly affects the catalytic efficiency of water electrolysis during hydrogen production. While the high cost of noble metal catalysts limits their engineering applications. Therefore, there is an urgent need to develop an economical and abundant catalyst with efficient OER performance to replace noble metal catalysts to reduce costs. In this work, we propose a method for the preparation of composite catalytic electrodes by magnetically induced jet electrodeposition. Ni–Co–CeO₂/Ni composite electrodes with a unique micro-nano structure and a large specific surface area were rapidly obtained through magnetically induced adsorption of nano-mixed particles. It was found that the Ni–Co–CeO₂/Ni composite electrode deposited by magnetically induced electrodeposition exhibited a lower overpotential of 301 mV@10 mA/cm² when the nano-mixed particle concentration was 2 g/L, and the corresponding Tafel slope was as low as 43.72 mV/dec. The key parameters of overpotential and Tafel slope reach or even outperform the best noble metal electrode in the industry, indicating that the Ni–Co–CeO₂/Ni composite electrode had excellent OER catalytic performance. The study demonstrates that magnetically induced jet electrodeposition provides a new method for the preparation of catalytic electrodes, which has important applications in the electrolysis of water for hydrogen production.     

Supported mesoporous Cu/CeO2-δ catalyst for CO2 reverse water–gas shift reaction to syngas

The design and development of a high performance hydrogenation catalyst is an important challenge in the utilization of CO₂ as resources. The catalytic performances of the supported catalyst can be effectively improved through the interaction between the active components and the support materials. The obtained results demonstrated that the oxygen vacancies and active Cu⁰ species as active sites can be formed in the Cu/CeO_2-δ catalysts by the H₂ reduction at 400 °C. The synergistic effect of the surface oxygen vacancies and active Cu⁰ species, and Cu⁰–CeO_2-δ interface structure enhanced catalytic activity of the supported xCu/CeO_2-δ catalysts. The electronic effect between Cu and Ce species boosted the adsorption and activation performances of the reactant CO₂ and H₂ molecules on the corresponding Cu/CeO_2-δ catalyst. The Cu/CeO_2-δ catalyst with the Cu loading of 8.0 wt% exhibited the highest CO₂ conversion rate in the RWGS reaction, reaching 1.38 mmol·g_cat⁻¹ min⁻¹ at 400 °C. Its excellent catalytic performance in the RWGS reaction was related to the complete synergistic interaction between the active species via Ce³⁺-□-Cu⁰ (□: oxygen vacancy). The Cu/CeO_2-δ composite material is a superior catalyst for the RWGS reaction because of its high CO₂ conversion and 100% CO selectivity.     

Partial oxidation of methane over CeO2 loaded hydrotalcite (MgNiAl) catalyst for the production of hydrogen rich syngas (H2, CO)

In this work, partial oxidation of methane (POM) was investigated using Mg-Ni-Al (MNA) hydrotalcite promoted CeO₂ catalyst in a fixed bed reactor. MNA hydrotalcite was synthesized using the co-precipitation process, while CeO₂ was incorporated via the wetness impregnation technique. The CeO₂@MNA samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDS), thermal gravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), and Brunauer-Emmett-Teller (BET) technique. The catalytic activity of CeO₂ promoted MNA (CeO₂@MNA) for POM reaction was evaluated for various CeO₂ loading kept the feed ratio CH₄/O₂ = 2 at 850 °C. The catalyst containing 10 wt% cerium loading (10%CeO₂@MNA) showed 94% CH₄ conversion with H₂/CO ratio above 2.0, that is more suitable for FT synthesis. The performance of catalyst is attributed to highly crystalline stable CeO₂@MNA with better Ce-MNA interactions withstand for 35 h time on stream. Furthermore, the spent catalyst was examined by TGA, SEM-EDS, and XRD to evaluate the carbon formation and structural changes during the span of reaction time.     

Water-gas shift of reformate streams over mono-metallic PGM catalysts

Mono-metallic Pt and Rh catalysts supported on both CeO₂ and TiO₂ were prepared and tested for water-gas shift activity in a Flowrence, high throughput reactor system. The feed composition mimicked a typical fuel processor, steam methane reformer outlet stream. The Pt/CeO₂ catalyst showed the best metal activity of ～3.8 E-07 moles CO converted·gPt^-1 s^-1, at a Pt loading of 0.5 wt%, activity decreasing with increasing metal loading. Furthermore, the Pt/CeO₂ catalyst produced almost no methane while the Rh based catalysts led to substantial methanation.     

A review on ethanol steam reforming for hydrogen production over Ni/Al2O3 and Ni/CeO2 based catalyst powders

Hydrogen is contemplated as an alternative clean fuel for the future. Ethanol steam reforming (ESR) is a carbon-neutral, sustainable, green hydrogen production method. Low cost Ni/Al₂O₃ and Ni/CeO₂ powder catalysts demonstrate high ESR activity. However, acidic nature of Al₂O₃ and instability of CeO₂ lead to deactivation of the catalysts easily. This article examines the research articles published on the modification of Ni by various noble and non-noble metals and on alteration of the supports by different metal oxides in detail and their effect on ESR all through 2000–2021. The ESR reaction mechanisms on Ni/Al₂O₃ and Ni/CeO₂ powder catalysts and basic thermodynamics for different possible reactions and H₂ yield are explored. Manipulation of catalyst morphology (surface area and particle size) via preparation method, selection of active metal promoter and support modifier are found to be significantly important for H₂ production and minimizing carbon deposition on catalysts.     

Influence of metal oxides on Pt catalysts for methanol electrooxidation using electrochemical impedance spectroscopy

Carbon nanotubes used as supports for platinum catalysts deposited with metal oxides (CeO₂, TiO₂, and SnO₂) were prepared for their application as anode catalysts in a direct methanol fuel cell. Cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy measurements were carried out in a solution of 0.5 M CH₃OH and 0.5 M H₂SO₄. Catalysts with the addition of CeO₂, TiO₂, and SnO₂ presented higher catalytic activity than pure platinum catalysts, and the catalysts with CeO₂ were the best among them. Electrochemical impedance spectra indicated that methanol electrooxidation on these catalysts had different impedance behaviors at different potential regions. The mechanism of methanol electrooxidation changed with increases of the potential. The promotion effect of the metal oxides lies in the oxidation of intermediate CO_ads on Pt at low potential regions.     

Effect of precipitation sequence on physicochemical properties of CeO2 support for hydrogen production from low-temperature water-gas shift reaction

A one-step reverse precipitation method has been developed to prepare nano-sized ceria (CeO₂) support with controlled physicochemical properties for low temperature water-gas shift (LT-WGS) reaction. The nano-sized CeO₂ support prepared by reverse precipitation method has a high Brunauer-Emmett-Teller (BET) surface area of 162.8 m²/g. To compare catalytic activity with that of CeO₂ prepared by normal precipitation method, 5 wt% Cu was employed as the active metal, coupled to the CeO₂ support. The catalytic activity of CeO₂ supported Cu catalyst prepared by reverse precipitation method was evaluated for the first time in LT-WGS reaction. Notably, the CeO₂ – R supported Cu catalyst, prepared by reverse precipitation method, showed higher CO conversion and turnover frequency (TOF) values than CeO₂–N supported Cu catalyst prepared by normal precipitation method.     

Pt/graphite catalyst for hydrogen generation by HI decomposition reaction in S–I thermochemical cycle

Hydrogen is an attractive energy carrier for future because of various reasons. Therefore its large scale production is the need of the hour. One of the ways to achieve this is sulfur iodine thermochemical cycle and HI decomposition reaction is one of the three reactions constituting the cycle. Pt/graphite catalysts with different loading of platinum were prepared by impregnating colloidal graphite with hexachloroplatinic acid solution followed by reduction under N₂ flow. The catalysts prepared have been characterized by X‐ray diffraction, Raman, scanning electron microscopy, X‐ray photoelectron spectroscopy and Brunauer–Emmett–Teller surface area. These catalysts have been employed for liquid phase HI decomposition under different conditions. To evaluate the stability of this catalyst against noble metal leaching under the reaction conditions, the eluent was analyzed by using ICP‐OES. Platinum loaded catalysts (0.5%, 1% and 2%) show 8.4%, 17.5% and 23.4% conversion respectively. From the present study we conclude that Pt/graphite is a suitable and stable catalyst for liquid phase HI decomposition reaction. Copyright © 2015 John Wiley & Sons, Ltd.     

Hydrogen production from low temperature WGS reaction on co-precipitated Cu–CeO2 catalysts: An optimization of Cu loading

Low temperature water–gas shift (WGS) reaction has been carried out at the gas hourly space velocity of 72,152 h⁻¹ over Cu–CeO₂ catalyst prepared by a co-precipitation method. Cu loading was optimized to obtain highly active co-precipitated Cu–CeO₂ catalysts for low temperature WGS. 80 wt% Cu–CeO₂ exhibited the highest CO conversion as well as the most stable activity (X_CO > 46% at 240 °C for 100 h). The excellent catalytic performance is mainly due to a strong metal to support interaction, resulting in the prevention of Cu sintering.     

Coking behavior of nickel and a rhodium based catalyst used in steam reforming for power-to-gas applications

This paper proposes partial steam reforming of natural gas as a chemical storage option for excess electricity. Thermodynamic simulations with Aspen Plus^® show that highest process efficiencies are reached at low steam-to-carbon (S/C) ratios in the feed. However, coke deposition due to unwanted side or follow-up reactions and thus catalyst deactivation is likely in this operation range. In an experimental evaluation three catalysts were selected to test their resistance towards coking: two nickel based and one rhodium based noble metal catalyst. They were tested regarding their long-term stability at S/C ratios as low as 0 to 0.1 and reaction temperatures between 450 and 500 °C. A different reaction and deactivation behavior was observed for nickel and the noble metal catalysts. The measured life times of the noble metal catalyst were by a factor of at least 100 higher than for the two selected nickel catalysts at the applied reforming conditions. Furthermore, after each reforming experiment, a temperature-programmed oxidation (TPO) analysis was performed for the spent catalysts. Based on literature data, the measured CO₂ peaks at corresponding temperatures were related to the different forms of solid carbon depositions. Main carbonaceous species found on the nickel catalysts were of filamentous nature, whereas one or two more reactive C species with monoatomic or polymeric structure at much lower amount were detected on the noble metal catalyst. Further SEM analysis confirmed these findings.     

Catalytic and DRIFTS study of the WGS reaction on Pt-based catalysts

The water–gas shift (WGS) activity of Pt/SiO₂, Pt/CeO₂ and Pt/TiO₂ catalysts was studied by in-situ diffuse reflection infrared Fourier transform spectroscopy (DRIFTS). Samples contained a similar amount of Pt, between 0.34 and 0.50%, and were characterized by employing a variety of physical and spectroscopic techniques. The catalyst activities were evaluated through both CO conversion versus temperature and CO conversion versus time tests. The DRIFTS spectra were obtained on stream during the WGS reaction at increasing temperatures, from 303 to 573 K. Reduced ceria was the only active support and promoted the WGS reaction on surface bridging OH groups that react with CO to form formate intermediates. Pt/SiO₂ was more active than CeO₂ and catalyzed the WGS reaction through a monofunctional redox mechanism on metallic Pt sites. The CO conversion turnover rate was more than one order of magnitude greater on Pt/CeO₂ than on Pt/SiO₂ showing that the reaction proceeds faster via a bifunctional metal-support mechanism. Platinum on Pt/CeO₂ increased the concentration of OH groups by increasing the ceria reduction extent and also provided a faster pathway for the formation of formate intermediates in comparison to CeO₂ support. Pt/TiO₂ catalysts were clearly more active than Pt/CeO₂. The WGS reaction on Pt/TiO₂ was catalyzed via a bifunctional metal-support mechanism, probably involving the activation of CO and water on the metal and the support, respectively. The role of platinum on Pt/TiO₂ was critical for promoting the reduction of Ti⁴⁺ ions to Ti³⁺ which creates oxygen vacancies in the support to efficiently activate water.     

Production and characterization of ITO-Pt semiconductor powder containing nanoscale noble metal particles catalytically active in dye-sensitized solar cells

Doped indium tin oxide (ITO) samples of a surface area around 60 m²/g have been synthesized. As doping component platinum and gold atoms were utilized, respectively. The powders were produced by pyrolyzing mixed metal oxide precursors in a first zone in a flame consisting of hydrogen and air, metering a noble metal compound and reducing gas into a second zone of the flame and separating off the solid obtained in a third zone. Well-defined solid phases In₂Pt and In₂Au in ITO were obtained, respectively. The production of a mixture with discrete SnO₂ entities could be avoided. The mixed oxide powder doped with platinum can be used as a catalyst. The structure and composition of materials obtained at different levels of platinum dosing into a flame reactor has been determined. The size of the noble metal-containing entities ranged at about 3.5–5.5 nm. The catalytic properties of these oxides containing noble metal have been utilized in the fabrication of dye-sensitized solar cells (DSCs). Long term stability of DSCs containing liquid electrolytes requires a glass sealing of the two electrodes at a temperature of over 600 °C. Such high temperatures are detrimental to the catalytic activity of the conventional platinum layers in the counter electrode. Improved catalytic activity could be achieved by platinum entities bound to indium tin oxide. This catalytic material can effectively be used in the DSCs with glass sealing, the sealing temperature being over 600 °C. Spray pyrolysis in a flame reactor is highly suitable to produce noble metal-containing oxides in one single production step. Platinum-containing ITO particles from flame pyrolysis production exhibit superior catalytic activity in dye-sensitized solar cells compared to material from conventional thermal decomposition.     

Supported catalysts for induction-heated steam reforming of methane

Ni₆₀Co₄₀ nanoparticles supported on γ-Al₂O₃ capable of simultaneously catalysing the steam reforming reaction of methane and supplying in-situ the heat necessary to activate the reaction by induction heating, have been synthesized and characterized. Energy is remotely and promptly supplied by an alternating radiofrequency magnetic field (induction heating system) to supported nanoparticles that act as dissipating agents by virtue of their ferromagnetic properties. The temperature reached on the Ni–Co based catalyst surface is high enough to obtain good catalytic performances for the steam methane reforming (SMR). By varying synthesis conditions, samples with two different metal loading (17 wt% and 30 wt%) and different particle size distribution were prepared and characterized. Experimental results evidence that the temperature reached on the catalyst surface is related to the metal loading and to the particles size distribution that strongly affect the ability of ferromagnetic nanoparticles to convert the externally applied radio frequency field into heat. Catalyst pellets proved their effectiveness reaching the temperature of 720 °C during SMR reaction and 80% methane conversion.     

Hydrogen production by partial oxidation of ethanol over Pt/CNT catalysts

The platinum‐supported catalysts have been prepared by ethylene glycol reduction method, and the catalysts were applied to the partial oxidation of ethanol (POE) for hydrogen production. Four types of support, including CNTs, Al₂O₃, ZrO₂, and CeO₂, were used on POE catalytic performance test. Prior to catalyst preparation, the influence of acidic pretreatment on CNTs purity, surface morphology, and pore structure were investigated. The acid‐treated CNTs and prepared catalysts were characterized with N₂ physisorption, Raman, thermogravimetric, and transmission electron microscopy analysis. The experimental results show that the particle size and metal dispersion of platinum on CNTs, as well as POE activity, depend on pH value of reducing agent and reduction temperature in the stage of catalyst preparation. In the condition pH value of 10 and temperature at 120 °C for catalyst 5 wt% Pt/CNTs preparation, 2 nm platinum clusters were obtained. Using the as‐prepared catalyst to study the effects of POE reaction conditions on the ethanol conversion, hydrogen selectivity, and hydrogen production rate under constant gas hourly space velocity, the corresponding values at the optimum reaction temperature 400 °C and O₂/C₂H₅OH molar ratio of 0.5 were 98.2%, 97.5%, and 202.3 mmol s^?1 kg^?1, respectively. Copyright © 2013 John Wiley & Sons, Ltd.     

Syngas production via dry reforming of methane over CeO2 modified Ni/Al2O3 catalysts

Syngas production via dry reforming of methane (DRM) was experimentally investigated using Ni-based catalyst. Ni/Al₂O₃ modification with CeO₂ addition and O₂ addition in the reactant were employed in this study to suppress carbon deposition and to enhance catalyst activity. It was found that DRM performance can be enhanced using CeO₂ modified Ni/Al₂O₃ catalyst due to CeAlO₃ formation. However, an optimum amount of CeO₂ loading exists to obtain the best DRM performance due to the decrease in specific surface area as the CeO₂ loading increases. Without O₂ addition, the reverse water-gas shift reaction plays an important role in DRM. It was found that CH₄ conversion and CO yield were enhanced while CO₂ conversion and H₂ yield are decreased as the CO₂ amount in feedstock increased in DRM. With O₂ addition in the fed reactant, it was found that the methane oxidation reaction plays an important role in DRM. CH₄ conversion can be enhanced by O₂ addition. However, decreases in CO₂ conversion and H₂ and CO yields occurred due to greater H₂O and CO₂ productions from the methane oxidation reaction. The thermogravimetric analysis (TGA) results showed that CeO₂ modified Ni/Al₂O₃ catalyst would have the lowest amount of carbon deposition when O₂ is introduced into the reaction.     

Highly efficient steam reforming of ethanol (SRE) over CeOx grown on the nano NixMgyO matrix: H2 production under a high GHSV condition

Steam reforming of ethanol (SRE) over non‐noble metal catalysts is normally conducted at high temperature (>600°C) to thermodynamically favour the catalytic process and carbon deposition mitigation. However, high temperature inhibits water‐gas shift reaction (WGSR) and therefore restrains the yield of H₂ and leads to the formation of an excessive amount of CO. The modification of non‐noble metal catalyst to enhance WGSR is an attractive alternative. In this study, CeO_x was firstly loaded onto a nano‐scaled Ni_xMg_yO matrix and subsequently used as the catalyst for hydrogen production via SRE. Morphology of the catalyst materials was characterized by using a series of technologies, while H₂‐temperature programmed reduction (H₂‐TPR), CO‐temperature programmed deposition (CO‐TPD), and X‐ray photoelectron spectroscopy (XPS), were employed to study the surface nickel, ceria clusters, and their interactions. The catalytic activity and durability of the catalyst were studied in the temperature region of 500°C to 800°C. The CeO_x‐coated nano Ni_xMg_yO matrix exhibited an outstanding hydrogen yield of 4.82 mol/mol_ethanol under a high gas hourly space velocity (GHSV) of 200 000 hour^?1. It is found that the unique Ni⁰‐CeO_x structure facilitates the adsorption of CO on the surface and therefore promotes the effective hydrogen production via WGSR. Moreover, this modified Ni_xMg_yO matrix was found to be a more robust and anticoking nanocatalyst because of reversible switch between Ce⁴⁺ and Ce³⁺.     

Ni/CeO2/ZSM-5 catalysts for the production of hydrogen from the pyrolysis–gasification of polypropylene

The production of hydrogen from the two-stage pyrolysis–gasification of polypropylene using a Ni/CeO₂/ZSM-5 catalyst has been investigated. Experiments were conducted on CeO₂ loading, calcination temperature and Ni loading of the Ni/CeO₂/ZSM-5 catalyst in relation to hydrogen production. The results indicated that with increasing CeO₂ loading from 5 to 30 wt.% for the 10 wt.% Ni/CeO₂/ZSM-5 catalyst calcined at 750 °C, hydrogen concentration in the gas product and the theoretical potential hydrogen production were decreased from 63.0 to 49.8 vol.% and 50.4 to 21.6 wt.%, respectively. In addition, the amount of coke deposited on the catalyst was reduced from 9.5 to 6.2 wt.%. The calcination temperature had little influence on hydrogen production for the catalyst containing 5 wt.% of CeO₂. However, for the 10 wt.% Ni/CeO₂/ZSM-5 catalyst with a CeO₂ content of 10 or 30 wt.%, the catalytic activities reduced when the calcination temperature was increased from 500 to 750 °C. The SEM results showed that large amounts of filamentous carbons were formed on the surface of the catalysts. The investigation of different Ni content indicates that the Ni/CeO₂/ZSM-5 ((2-10)-5-500) catalyst containing 2 wt.% Ni showed poor catalytic activity in relation to the pyrolysis–gasification of polypropylene according to the theoretical potential H₂ production (7.2 wt.%). Increasing the Ni loading to 5 or 10 wt.% in the Ni/CeO₂/ZSM-5 ((2-10)-5-500) catalyst, high potential hydrogen production was obtained.     

CeO2 nanoparticles improved Pt-based catalysts for direct alcohol fuel cells

We developed an ultrasonic co-deposition technique to enhance the activity of Pt/C catalyst (and Pt/CNT, PtRu/C catalysts) for direct alcohol fuel cells (DAFCs) by CeO₂ nanoparticles. The composite catalyst architecture is obtained by an ultrasonically mixing commercial Pt/C catalyst and CeO₂ nanoparticles. Both Pt and CeO₂ are dispersed uniformly in the electrodes resulting in a great deal of CeO₂–Pt–C triple junction interfaces. Unlike traditional preparation of metal oxide supported Pt catalysts, CeO₂ will not cut the connection between Pt and C in this composite catalyst structure. Electrochemical measurements confirm that CeO₂ can improve almost all Pt based catalysts (Pt/C, Pt/CNT, and PtRu/C) for almost all small molecular alcohols (methanol, ethanol, ethylene glycol, and glycerol) electro-oxidation. EIS measurement shows that reaction resistance between Pt and alcohols is decreased much by adding small CeO₂ nanoparticles. Besides, these composite catalysts have high stability. It proves CeO₂ a very promising co-catalyst of Pt based catalysts for DAFCs.