Hydrogen production from ethanol steam reforming over Ni/SiO2 catalysts: A comparative study of traditional preparation and microwave modification methods

Four silica‐supported nickel catalysts with Ni content of 10 wt% were prepared by impregnation and coprecipitation methods with or without microwave‐assisted calcination. The prepared catalysts were characterized by some techniques (BET, XRD, TEM, XPS, H₂‐TPR, etc.) and evaluated with respect to steam reforming of ethanol (SRE) for hydrogen production. The results show that the prepared Ni/SiO₂ catalysts are all very active and selective for SRE. The high activity of the four catalysts may benefit from their high specific areas and the good dispersion of active components on the carrier. The rate of carbon deposition decreases with reaction temperature especially below 450 °C. The maximum hydrogen yield of 4.54 mol H₂/mol EtOH‐reacted can be obtained over the Ni/SiO₂ catalyst by the microwave‐assisted coprecipitation method at a reaction temperature of 600 °C, EtOH/H₂O molar ratio of 1:12, liquid hourly space velocity of 11.54 h^?1 and time on stream within 600 min. The Ni/SiO₂ catalysts with microwave modification exhibits better performances of hydrogen production, stability and resistance to carbon deposition than that without microwave modification preparation, which is mainly attributed to that the microwave‐assisted treatment can decrease the catalyst acidity and enhance the interaction between metal support. Copyright © 2013 John Wiley & Sons, Ltd.     

Ethanol steam reforming on Ni/CaO catalysts for coproduction of hydrogen and carbon nanotubes

Catalytic steam reforming of ethanol is considered as a promising technology for producing H₂ in the modern world. In this study, using a fixed‐bed reactor, steam reforming of ethanol was performed for production of carbon nanotubes (CNTs) and H₂ simultaneously at 600°C on Ni/CaO catalysts. Commercial CaO and a synthetic CaO prepared using sol‐gel were scrutinized for ethanol's catalytic steam reforming. Analysis results of N₂ isothermal adsorption indicate that the CaO synthesized by sol‐gel has more pore volume and surface area in comparison with the commercial CaO. When Ni was loaded, the Ni/CaO catalyst shows an encouraging catalytic property for H₂ production, and an increase in Ni loading could improve H₂ production. The Ni/CaO catalyst with sol‐gel CaO support has presented a higher hydrogen production and better catalytic stability than the catalysts with the commercial CaO support at low Ni loading. The highest hydrogen yield is 76.8% at Ni loading content of 10% for the Ni/sol‐gel CaO catalyst with WHSV of 3.32/h and S/C ratio of 3. The carbon formed after steam reforming primarily consists of filamentous carbons and amorphous carbons, and CNTs are the predominant type of carbon deposition. The deposited extent of carbon on the used Ni/CaO catalyst lessen upon more Ni loading, and the elongated CNTs are desired to be formed at the surface of the Ni/sol‐gel CaO catalyst. Thus, an efficient process and improved economic value is associated with prompt hydrogen production and CNTs from ethanol steam reforming.     

Hydrogen from steam reforming of ethanol in low and middle temperature range for fuel cell application

The catalyst, Ni nano-particles supported on Y₂O₃, which was prepared by three methods, was studied. The structural properties of the catalysts were tested through X-ray diffraction and BET area. The catalyst of Ni/Y₂O₃ exhibits high activity for ethanol steam reforming with conversion of ethanol of 98% and selectivity of hydrogen of 38% at 300°C, conversion of ethanol of 98% and selectivity of hydrogen of 55% at 380°C. With temperature increasing to and above 500°C, the conversion of ethanol increased to 100%, but the selectivity of hydrogen did not increase so much, it was 58% at 600°C. The catalyst has long-term stability for steam reforming of ethanol and is a good choice for ethanol processors for fuel cell applications.     

Hydrogen‐rich gas production from ethanol steam‐reforming reaction using NiZr‐loaded MCM‐48 catalysts at mild temperature

The rich‐hydrogen generation from ethanol steam reforming over NiZr, which is used as an anode material in solid oxide fuel cells, ‐loaded MCM‐48 (NiZr/MCM‐48) catalyst was investigated in this study. We used an impregnation approach to synthesize an MCM‐48 (70.0 wt‐%) support loaded with bimetallic NiZr (30.0‐wt%, Ni:Zr atomic ratio = 4:6, 5:5, and 6:4), and the prepared catalysts were applied to the steam‐reforming reactions of ethanol. These three bimetallic NiZr/MCM‐48 catalysts exhibited significantly higher reforming reactivity than the mono‐metal, Ni‐loaded MCM‐48 (Ni/MCM‐48) catalyst. The hydrogen production was started from 350°C over the three NiZr/MCM‐48 catalysts, compared to above 550°C over the Ni/MCM‐48 catalyst. The catalytic performance was affected by the Zr content. The H₂ production and ethanol conversion were maximized at 85% and 95%, respectively, over Ni₄Zr₆/MCM‐48 at 750°C for 1 h at CH₃CH₂OH:H₂O = 1:1 and a gas hourly space velocity of 4000 h^‐1. This high performance was maintained for up to 60 h. Copyright © 2013 John Wiley & Sons, Ltd.     

Tungsten nitride decorated CNTs as efficient hybrid supports for PtRh alloys in electrocatalytic ethanol oxidation

Direct ethanol fuel cells (DEFCs) offer an attractive alternative to fossil fuel-powered devices due to their high energy density and environmental benignity. However, high cost and poor stability of catalysts are still the main obstacles for the commercialization of DEFCs. Herein, a novel catalyst comprising PtRh alloys anchored on carbon nanotubes that decorated with tungsten nitride (Pt₉Rh-WN/CNTs) was synthesized via impregnation-reduction method and followed by thermal annealing in N₂. The X-ray powder diffraction (XRD), scanning electron micrograph (SEM) and transmission electron microscopy (TEM) are employed to characterize the corresponding physico-chemical properties of the as-prepared catalysts. Electrocatalytic performance for ethanol oxidation is evaluated by cyclic voltammetry, linear scan voltammetry, CO-stripping voltammograms, chronoamperometry and chronopotentiometry. The current density on Pt₉Rh-WN/CNTs is 484.8 mA mg_Pt^?1, which is much higher than that of Pt₉Rh/CNTs (305.7 mA mg_Pt^?1) and Pt/CNTs (135.1 mA mg_Pt^?1). Most importantly, the onset potential for CO oxidation on Pt₉Rh-WN/CNTs is 0.27 V, which is more negative than that on Pt₉Rh/CNTs (0.37 V) and Pt/CNTs (0.40 V). Therefore, the Pt₉Rh-WN/CNTs catalyst displays both outstanding catalytic activity and excellent CO-poisoning tolerance for ethanol oxidation. Synergistic effects arising between WN and PtRh alloy along with nitrogen-doping effects of CNTs with ammonia are proposed to contribute to the outstanding performance of this catalyst in ethanol oxidation.     

Effects of catalyst preparation route and promoters (Ce and Zr) on catalytic activity of CuZn/CNTs catalysts for hydrogen production from methanol steam reforming

Ce or Zr promoted CuZn/CNTs (carbon nanotubes) catalysts were synthesized by microwave-assisted polyol, co-precipitation and impregnation methods and were used to generate hydrogen by methanol steam reforming (MSR) process. The physico-chemical properties of the prepared catalysts were analyzed by BET, XRD, FT-IR, TEM, FE-SEM, EDX-dot mapping and H₂-TPR methods. The effect of various operating parameters on methanol conversion and selectivity of gaseous products was investigated. The results indicated that the addition of 2 wt% CeO₂ promoter on CuZn/CNTs catalyst synthesized by impregnation route (CuZn/CNTs (Imp)) increased its methanol conversion from 81.3 to 85.2%, and decreased its CO selectivity from 6.2 to 3.8% at 300 °C, WHSV of 7.5 h^?1 and S/C molar ratio of 2. In addition, the CeCuZn/CNTs catalyst prepared via the microwave-assisted polyol route (CeCuZn/CNTs (Pol)) exhibited the best catalytic activity with 98.2% hydrogen selectivity, 2.6% CO selectivity and 94.2% methanol conversion at 300 °C. Furthermore, a 48 h continuous MSR reaction at 300 °C, identified CeCuZn/CNTs (Pol) as the most stable catalyst due to its higher metal particle dispersion and better interaction between the active phase and the CNTs support.     

Na-intercalated carbon nanotubes-supported platinum nanoparticles as new highly effective catalysts for preferential CO oxidation in H2-rich stream

Na⁺-intercalated carbon nanotubes (Na-CNTs) were obtained by impregnation of CNTs with sodium acetate followed by annealing at high temperatures under argon. Stable Na-CNTs-supported Pt catalysts (Pt/Na-CNT catalysts) were then prepared for hydrogen purification via preferential CO oxidation in a H₂-rich stream (CO-PROX). Characteristic studies show that the content of Na⁺ species in CNTs is increased with increased annealing temperature and the Pt nanoparticles with an average size of 2–3 nm are uniformly dispersed on the surfaces of Na-CNTs. An optimized Pt/Na-CNT catalyst with 5 wt% Pt loading can completely remove CO from 40 °C to 200 °C. This catalyst also exhibits long-term stability for 1000 h at 100 °C in feed gas containing 1% CO, 1% O₂, 50% H₂, 15% CO₂, and 10% H₂O balanced with N₂. The electron transfer between the Pt nanoparticles and Na⁺ species plays an important role in enhancing the CO-PROX performance of the catalyst.     

Highly efficient and stable bifunctional electrocatalyst for water splitting on Fe–Co3O4/carbon nanotubes

Replacement of precious platinum (Pt) or ruthenium oxide (RuO₂) catalysts with efficient, cheap and durable electrocatalysts from earth-abundant elements bifunctional alternatives would be significantly beneficial for key renewable energy technologies including overall water splitting and hydrogen fuel cells. Despite tremendous efforts, developing bifunctional catalysts with high activity at low cost still remain a great challenge. Here, we report a nanomaterial consisting of core-shell-shaped Fe–Co₃O₄ grown on carbon nanotubes (Fe–Co₃O₄/CNTs) and employed as a bifunctional catalyst for the simultaneous electrocatalysts on oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). The Fe–Co₃O₄/CNTs electrocatalyst outperforms the commercial RuO₂ catalyst in activity and stability for OER and approaches the performance of Pt/C for HER. Particularly, it shows superior electrocatalytic activity with lowering overpotentials of 120 mV at 10 mA cm^?2 for HER and of 300 mV at 10 mA cm^?2 for OER in 1 M KOH solution. The superior catalytic activity arises from unique core-shell structure of Fe–Co₃O₄ and the synergetic chemical coupling effects between Fe–Co₃O₄ and CNTs.     

CNT-based catalysts for H2 production by ethanol reforming

Hydrogen production by steam reforming of ethanol (SRE) was studied using steam-to-ethanol ratio of 3:1, between the temperature range of 150–450 °C over metal and metal oxide nanoparticle catalysts (Ni, Co, Pt and Rh) supported on carbon nanotubes (CNTs) and compared to a commercial catalyst (Ni/Al₂O₃). The aim was to find out the suitability of CNTs supports with metal nanoparticles for the SRE reactions at low temperatures. The idea to develop CNT-based catalysts that have high selectivity for H₂ is one of the driving forces for this study. The catalytic performance was evaluated in terms of ethanol conversion, product gas composition, hydrogen yield and selectivity to hydrogen. The Co/CNT and Ni/CNT catalysts were found to have the highest activity and selectivity towards hydrogen formation among the catalysts studied. Almost complete ethanol conversion is achieved over the Ni/CNT catalyst at 400 °C. The highest hydrogen yield of 2.5 is, however, obtained over the Co/CNT catalyst at 450 °C. The formation of CO and CH₄ was very low over the Co/CNT catalyst compared to all the other tested catalysts. The Pt and Rh CNT-based catalysts were found to have low activity and selectivity in the SRE reaction. Hydrogen production via steam reforming of ethanol at low temperatures using especially Co/CNT catalyst has thus potential in the future in e.g. the fuel cell applications.     

Hydrogen‐rich gas production from catalytic gasification of pine sawdust over Fe‐Ce/olivine catalyst

In order to improve hydrogen production and reduce tar generation during the biomass gasification, a catalyst loaded Fe‐Ce using calcined olivine as the support (Fe‐Ce/olivine catalysts) was prepared through deposition‐precipitation method. The characteristics of catalysts were determined by XRF, BET, XRD, and FTIR. Syngas yield, hydrogen yield, and tar yield were used to evaluate the catalyst activity. Meanwhile, the stability of catalysts was also studied. The results showed that the specific surface area and pore volume of olivine after calcined at high temperature were improved which was beneficial for the load of metals. α‐Fe₂O₃ and CeO₂ were the main active component of Fe‐Ce/olivine catalyst. The Fe‐Ce/olivine catalyst displayed a good performance on the catalytic gasification of pine sawdust with a syngas yield of 0.93 Nm³/kg, H₂ yield of 21.37 mol/kg, and carbon conversion rate of 55.14% at a catalytic temperature and gasification temperature of 800°C. Meanwhile, the Fe‐Ce/olivine catalyst could maintain a good stability after 150 minutes used.     

Highly efficient CoB catalyst using a support material based on Spirulina microalgal strain treated with ZnCl2 for hydrogen generation via sodium borohydride methanolysis

In the study, a different support material based on ZnCl₂‐treated Spirulina microalgal strain (SSMS‐ZnCl₂) was prepared. Then, the SSMS‐ZnCl₂‐CoB catalysts were used as a very efficient catalyst to produce hydrogen via the SB methanolysis. The SB concentration, Co metal percentage in the supported‐catalyst, ZnCl₂ concentration, ZnCl₂ impregnation time, temperature, and reusability experiments were performed. The maximum hydrogen generation rates (HGR) for the SSMS‐ZnCl₂‐CoB at 30°C and 60°C were found to be 9266 and 36 366 mL min^?1 g_cat^?1, respectively. In addition, TOF values for 30°C and 60°C were calculated 33 and 110 L·mol_H2·mol_Co^?1·min^?1 for the methanolysis of SB with SSMS‐ZnCl₂‐CoB catalyst. The activation energy was 31.13 kJ mol^?1. The reusability experiments were repeated five times under the same conditions. The almost 100% conversion was obtained at each use. XRD, FTIR, TEM, SEM‐EDX, and ICP‐MS analysis were performed for SSMS‐ZnCl₂‐CoB characterization.     

Dual-production of nickel foam supported carbon nanotubes and hydrogen by methane catalytic decomposition

Uniformly dispersed Ni catalysts supported on SiO₂ wash-coated Ni foams were synthesized by the wet impregnation method and successfully applied for methane catalytic decomposition (MCD) at atmospheric pressure. All the prepared catalysts exhibited high catalytic stability. The effects of reaction temperature, space velocity, Ni loading on the MCD performance and the morphologies of the as-prepared CNTs were investigated. The results show that high reaction temperature, low space velocity, and high Ni loading enhanced the hydrogen concentration in the outlet gases. Additionally, SEM and TEM observations indicate that the size (diameter) distribution of the as-prepared CNTs became broader with increasing reaction temperature and Ni loading, respectively. The uniform nickel-foam-supported CNTs and relatively high concentration of hydrogen were obtained simultaneously at 650 °C and at a weight hourly space velocity of 1 L g⁻¹_cat h⁻¹ by the catalyst with 20 wt% Ni. Raman spectroscopy reveals that the uniform MCNTs had a high degree of amorphization.     

Steam reforming of ethanol to hydrogen over nickel metal catalysts

In the present work acid‐treated Ni catalyst was investigated for the steam reforming (SR) of bio‐ethanol. Influential factors, such as reaction temperature, water‐to‐ethanol molar ratio and liquid hourly space velocity (LHSV), were investigated. The conversions were always complete at temperatures above 773 K, regardless of the changes of the reaction conditions. The yield to hydrogen increased with the increase in temperature and H₂O/C₂H₅OH molar ratios. The hydrogen yield up to 84% was reached under conditions: 923 K, LHSV of 5.0 ml g⁻¹ h⁻¹, H₂O/C₂H₅OH ratio of 10 over the acid‐treated Ni catalyst. The effects of the influential factors on the side reactions and the distribution of byproducts were discussed. Copyright © 2010 John Wiley & Sons, Ltd.     

Production of hydrogen by ethanol steam reforming over nickel–metal oxide catalysts prepared via urea–nitrate combustion method

A series of Ni/MgO catalysts have been prepared by a urea–nitrate combustion method, studied for the ethanol steam reforming, and compared with Ni/ZnO and Ni/Al₂O₃. The results show that Ni/MgO is superior to the latter two types of catalysts, especially in terms of H₂ yield. Influential factors, including Ni loading, temperature, water‐to‐ethanol molar ratio, and liquid hourly space velocity, are investigated with the Ni/MgO catalyst. The conversions are always complete at temperatures above 773 K, regardless of the changes of the other reaction conditions. The hydrogen yield increases with increasing temperature and H₂O/C₂H₅OH molar ratios, with up to 75% being obtained at 873 K, liquid hourly space velocity (LHSV) of 5.0 ml g^–1 h^–1 and H₂O/C₂H₅OH molar ratio of 10. Copyright © 2010 John Wiley & Sons, Ltd.     

Effect of phosphoric acid and acetic acid addition on the hydrogen evolution using Ni based catalyst prepared in ethanol,methanol, and water solvents

Ni-based catalysts were synthesized in water, methanol and ethanol solvents by chemical reduction with sodium borohydride (NaBH₄). The obtained catalyst for the first time was used to catalyze the NaBH₄ hydrolysis reaction with phosphoric acid and acetic acid including different concentrations. The maximum hydrogen production rates obtained in the hydrolysis reaction including 0.5 M phosphoric acid and 0.1 M acetic acid of the Ni-based catalyst prepared in ethanol solvent were 5214 and 3650 ml g^?1 min^?1, respectively.     

La2O3-modified highly dispersed AuPd alloy nanoparticles and their superior catalysis on the dehydrogenation of formic acid

Formic acid (FA, HCOOH), a convenient and safe hydrogen storage material, has the great potential for fuel cell applications. However, hydrogen generation of FA is inefficient in the presence of heterogeneous catalysts at relatively low temperatures, which remains a big challenge. Herein, La₂O₃-modified highly dispersed AuPd alloy nanoparticles (AuPdLa₂O₃) with small particle size have been successfully anchored on carbon nanotubes (CNTs) by a facile co-reduction route. Moreover, the catalyst exhibits excellent catalytic activity and 100% hydrogen selectivity for hydrogen generation in the formic acid/sodium formate (FA/SF) system with the initial turnover frequency (TOF) value of 589 mol H₂ mol^?1 catalyst h^?1 at 50 °C and 280 mol H₂ mol^?1 catalyst h^?1 even at room temperature (25 °C). The present Au_0.3Pd_0.7-(La₂O₃)_0.6/CNTs with superior catalysis on FA dehydrogenation without any CO generation at room temperature can not only pave the way for practical application of hydrogen storage system, but also can be extended to other catalysis system.     

A possible future fuel cell: the peroxide/peroxide fuel cell

Hydrogen peroxide (H₂O₂) and the reduction/oxidation by‐products of peroxide are non‐toxic to humans and the environment. Simple, low‐concentration hydrogen‐peroxide solutions used as fuel and direct peroxide/peroxide fuel cells (DPPFCs) face significant challenges in the development of a new class of power generators. A power density of 10 mWcm^?2 at a cell potential of 0.55 V have been achieved with a DPPFC composed of carbon‐paper‐supported nickel as the anode catalyst and carbon‐paper PbSO₄ as the cathode catalyst. The catalysts have been prepared by electroless deposition. Using non‐precious metals rather than platinum in our FC makes the cell cost effective comparable to that of PEMFCs. Additionally, as a low‐price fuel, H₂O₂ reduces the cost of this FC. Copyright © 2012 John Wiley & Sons, Ltd.     

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.     

Hydrogen production by auto-thermal reforming of ethanol over Ni catalysts supported on ZrO2: Effect of preparation method of ZrO2 support

Zirconia supports were prepared by a sol–gel method (S-ZrO₂) and by a templating sol–gel method (M-ZrO₂). Nickel catalysts supported on zirconia were then prepared by an incipient wetness impregnation method for use in hydrogen production by auto-thermal reforming of ethanol. For comparison, a commercial zirconia (C-ZrO₂) was also employed as a support for nickel catalyst. The effect of preparation method of zirconia on the catalytic property and catalytic performance of supported nickel catalysts (Ni/C-ZrO₂, Ni/S-ZrO₂, and Ni/M-ZrO₂) was investigated. The crystalline and physical property of zirconia supports and the catalytic performance of supported nickel catalysts were strongly affected by the preparation method of zirconia. BET surface area and pore volume were decreased in the order of M-ZrO₂ > S-ZrO₂ > C-ZrO₂. Both M-ZrO₂ and S-ZrO₂ supports showed only tetragonal phase of ZrO₂, while C-ZrO₂ support exhibited tetragonal and monoclinic phases of ZrO₂. Crystalline size of nickel species in the Ni/ZrO₂ catalysts decreased with increasing surface area and pore volume of ZrO₂ supports. All the Ni/ZrO₂ catalysts exhibited 100% conversion of ethanol at 500 °C, while product distributions over the Ni/ZrO₂ catalysts were different depending on the preparation method of zirconia. Among the catalysts tested, the Ni/M-ZrO₂ catalyst showed the best catalytic performance in hydrogen production by auto-thermal reforming of ethanol. Well developed mesopore, high surface area, and pure tetragonal phase of ZrO₂ were responsible for fine nickel dispersion and high catalytic performance of Ni/M-ZrO₂. C–C bond cleavage reaction and methane steam reforming reaction were also accelerated over the Ni/M-ZrO₂ catalyst.     

High-purity hydrogen production by sorption-enhanced methanol steam reforming over a combination of Cu–Zn–CeO2–ZrO2/MCM-41 catalyst and (Li–Na–K) NO3·MgO adsorbent

In this study, sorption-enhanced methanol steam reforming (SEMSR) was applied to generate high-purity hydrogen. The mesoporous MCM-41 as support and CuO, ZnO, CeO₂, ZrO₂ as active agents and promoters were employed for the catalyst preparation. In addition, (Li–Na–K) NO₃·MgO as a CO₂ adsorbent was prepared by the wet mixing method. The fresh and used catalysts were characterized by XRD, BET, FTIR, FESEM, TEM, H₂-TPR and TGA analyses. Also, the CO₂ sorbent was studied by XRD, BET, FESEM, TEM and TGA analyses before and after the reaction. The SEMSR performances of the synthesized catalyst and adsorbent were evaluated experimentally in a fixed-bed reactor. The effect of various conditions such as temperature, WHSV, feed molar ratio and sorbent/catalyst ratio were investigated. The best results were obtained at 300 °C, a feed molar ratio (water/methanol) of 2:1, a WHSV of 1.62 h^?1, and the sorbent/catalyst ratio of 8:1, which produced 99.8% hydrogen, 25% more than the hydrogen production during conventional methanol steam reforming. Moreover, the cyclic stability of the catalyst and the sorbent was studied for 10 cycles.