Kinetics of non-premixed hydrogen–oxygen catalytic recombination reaction at ambient temperature

This study proposes the use of the hydrogen–oxygen catalytic recombination reaction to safely eliminate the leaked hydrogen in a confined environment. Experiments on the hydrogen–oxygen reaction catalyzed by using Pt/C as a catalyst are conducted at ambient temperature in a small cylindrical vessel. The macroscopic kinetic process of the hydrogen–oxygen recombination reaction is investigated, and the effects of the reaction parameters, such as the initial hydrogen volume fraction and catalyst layer position, on the reaction temperature and hydrogen conversion are examined. The reaction temperature and temperature rise rate are shown to reach the maximum values when the initial hydrogen fraction is 70 vol%. When the initial hydrogen fraction is ≤ 67 vol%, the hydrogen conversion reaches 100%. After the initial hydrogen fraction is > 67 vol%, the hydrogen conversion decreases significantly, and the hydrogen conversion is only 53% for the initial hydrogen fraction is up to 80 vol%. Moreover, the position of the catalyst layer has a significant effect on the reaction rate and heat distribution inside the vessel. When the catalyst layer is near the bottom of the reaction vessel, the reaction rate is accelerated and the released heat accumulates at the bottom of the vessel. The influence law of the aforementioned factors can provide a technical reference for applications of the hydrogen–oxygen catalytic reaction.     

Challenges arising from the use of TiO2/rGO/Pt photocatalysts to produce hydrogen from crude glycerol compared to synthetic glycerol

Photoreforming has emerged as a novel technology expected to obtain chemical energy through solar energy transformation. In this way, sustainable valorization of glycerol, a biodiesel by-product, to clean fuels is a promising alternative to help meet the world's growing energy demand. In this work, TiO₂/rGO(x)/Pt(y) photocatalysts have been developed for hydrogen production from synthetic and crude glycerol solutions. The effect of several key operating parameters (including vol% of glycerol, pH, catalyst loading, wt% of GO, wt% of Pt, temperature, and light source) on hydrogen production rate has been studied. The results indicated different optimal operating parameters depending on glycerol origin, achieving up to 70.8 and 12.7 mmol h⁻¹ g⁻¹ of hydrogen using synthetic glycerol and crude glycerol, respectively. Additionally, GO nanosheets and Pt nanoparticles strongly influenced the hydrogen production rate but not the overall reaction mechanism. Impurities contented in crude glycerol are key factors in developing realistic hydrogen production processes.     

Preparation of Pt/Ce–Zr–Y mixed oxide/anodized aluminium oxide catalysts for hydrogen passive autocatalytic recombination

The use of a Pt-based catalyst was evaluated for autocatalytic hydrogen recombination. The Pt was supported on a mixture of Ce-, Zr- and Y-oxides (CZY) to yield nanosized Pt particles. The Pt/CZY/AAO catalyst was then prepared by the spray-deposition of the Pt/CZY intermediate onto an anodized aluminium oxide (AAO) layer on a metallic aluminum core. The Pt/CZY/AAO catalyst (3 × 1 cm) was evaluated for hydrogen combustion (1–8 vol% hydrogen in the air) in a recombiner section testing station. The thermal distribution throughout the catalyst surface was investigated using an infrared camera. The maximum temperature gradient (ΔT) for the examined hydrogen concentrations did not exceed 36 °C. The Pt/CZY/AAO catalyst was also evaluated for prolonged hydrogen combustion duration to assess its durability. An average combustion temperature of 239.0 ± 10.0 °C was maintained for 53 days of catalytic hydrogen combustion, suggesting that there was limited, or no, catalyst deactivation. Finally, a Pt/CZY/AAO catalytic plate (14.0 × 4.5 cm) was prepared to investigate the thermal distribution. An average surface temperature of 212.5 °C and a maximum ΔT of 5.4 °C was obtained throughout the catalyst surface at a 3 vol% hydrogen concentration.     

Smart nanocatalyst for ammonia-borane hydrolysis: Thermo-controlled hydrogen generation

A smart catalyst was fabricated by combining ordered mesoporous silica, Pt nanoparticles with ultra-small size (<2 nm), decatungstoeuropate and thermo-responsive polymer. Due to the coating of thermo-sensitive polymer and loading of Pt nanoparticles, the catalyst shows the thermo-controlled catalytic activity in the release of hydrogen from ammonia borane. For example, the catalyst has high catalytic activity at room temperature, showing catalytic “on” state. However, the hydrogen generation can be obviously suppressed at high temperature, showing catalytic “off” state. Furthermore, the composite hydrogel shows the switchable red luminescence in solution at high/low temperatures, which offers the possibility to track catalyst and understand catalytic mechanism. The thermo-controllable system of hydrogen generation has great potential applications in the safe hydrolysis from chemical hydride fuel. The smart catalyst could automatically decrease the release of hydrogen when the temperature of fuel system is high.     

One-step synthesis of Ni/yttrium-doped barium zirconates catalyst for on-site hydrogen production from NH3 decomposition

On-site produced hydrogen from ammonia decomposition can directly fuel solid oxide fuel cells (SOFCs) for power generation. The key issue in ammonia decomposition is to improve the activity and stability of the reaction at low temperatures. In this study, proton-conducting oxides, Ba(Zr,Y) O_3-δ (BZY), were investigated as potential support materials to load Ni metal by a one-step impregnation method. The influence of Ni loading, Ba loading, and synthesis temperature, of Ni/BZY catalysts on the catalytic activity for ammonia decomposition were investigated. The Ni/BZY catalyst with Ba loading of 20 wt%, Ni loading of 30 wt%, and synthesized at 900 °C attained the highest ammonia conversion of 100% at 600 °C. The kinetics analysis revealed that for Ni/BZY catalyst, the hydrogen poisoning effect for ammonia decomposition was significantly suppressed. The reaction order of hydrogen for the optimized Ni/BZY catalyst was estimated as low as ?0.07, which is the lowest to the best of our knowledge, resulting in the improvement in the activity. H₂ temperature programmed reduction and desorption analysis results suggested that a strong interaction between Ni and BZY support as well as the hydrogen storage capability of the proton-conducting support might be responsible for the promotion of ammonia decomposition on Ni/BZY. Based on the experimental data, a mechanism of hydrogen spillover from Ni to BZY support is proposed.     

Synthesis of Ni/TiO2 catalyst by sol-gel method for hydrogen production from sodium borohydride

Hydrogen is a sustainable, renewable and clean energy carrier that meets the increasing energy demand. Pure hydrogen is produced by the hydrolysis of sodium borohydride (NaBH₄) using a catalyst. In this study, Ni/TiO₂ catalysts were synthesized by the sol-gel technique and characterized by X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) methods. The effects of Ni loading ratio (20–40%), catalyst amount (75–200 mg), the concentration of sodium hydroxide (NaOH, 0.25–1 M), initial amount of NaBH₄ (75–125 mg) and the reaction temperature (20–60 °C) on hydrogen production performance were examined. The hydrogen yield (100%) and hydrogen production rate (110.87 mL/g_cat.min) were determined at the reaction conditions of 5 mL of 0.25 M NaOH, 100 mg NaBH₄, 100 mg Ni/TiO₂, 60 °C. Reaction order and activation energy were calculated as 0.08 and 25.11 kJ/mol, respectively.     

Effect of anolyte pH and cathode Pt loading on electricity and hydrogen co-production performance of the bio-electrochemical system

In a novel bio-electrochemical system (BES) for hydrogen and electricity co-production with acetate substrate, the anolyte pH and cathode Pt loading effects are investigated to improve the cell performance for hydrogen and electricity co-production and reduce the cost. The optimized anolyte pH is 9. The maximum hydrogen production rate of 0.55 m³ m⁻³ d⁻¹ and COD removal of 76% are obtained under optimal anolyte pH in the present BES. Over high or over low anolyte pH decreases the hydrogen production rate and COD removal. In addition, the experiments show that there is no considerable difference for the power density output and steady state current when the Pt catalyst loading is above 0.1 mg cm⁻². But when the Pt catalyst loading is lower than 0.1 mg cm⁻², the power density output and current decreases significantly. About 1.7 W m⁻³ power density output can be obtained by using 0.1 mg cm⁻² Pt catalyst in the present research.     

Synthesis of Pt nano catalyst in the presence of carbon monoxide: Superior activity towards hydrogen evolution reaction

The effect of carbon monoxide (CO) on the reduction of Pt ion to metallic Pt is studied. The modified GC electrode with platinum metal synthesized in the presence of CO shows excellent activity for hydrogen evolution reaction (HER). Despite the decrease in the loading of platinum (4.5 × 10⁻⁴ mg cm⁻²) a substantial increase in its electrocatalytic activity towards HER is observed in a sulfuric acid environment. The observed electrocatalytic activity is comparable to available commercial catalysts like Pt/C. Tafel slope was obtained to be 34 mV.dec^−1, and the overpotential was acquired to be 31 mV at the mass activity of 10 mA mg⁻¹ were observed which was very close to kinetic parameters of Pt/C catalyst.     

Molybdenum/graphene – Based catalyst for hydrogen evolution reaction synthesized by a rapid photothermal method

Catalysis of the hydrogen evolution reaction (HER) is important in the development of an energy economy based on clean hydrogen gas. In this work, we report a new catalyst material for the generation of hydrogen via hydronium reduction. The new material, which consists of MoO₂, sulfur, and graphene, was prepared by co-reduction of molybdenum salt and graphite oxide in air in the presence of focused solar radiation. The potential utility of this material for HER catalysis was evaluated by cyclic and linear-sweep voltammograms and compared against a Pt/C commercial catalyst. The MoO₂/graphene hybrid nanocomposite exhibits a Tafel slope of 47 mV/dec and hydrogen evolution at a potential only ∼120 mV more negative than the standard Pt/Carbon catalyst at 10 mA/cm² current density. The hydrogen gas generated by the catalytic material was measured using gas chromatography. The simple synthesis and low overpotential suggests that this hybrid composite has potential as an HER catalyst.     

Recombination of hydrogen-air catalyzed by Pt/C catalyst in a confined vessel at ambient temperature

Most of the previous studies have investigated the detonation and combustion characteristics of hydrogen and air mixtures, but the change process of hydrogen-air recombination reaction at ambient temperature is unclear. In this study, the variation of temperature and hydrogen conversion during the H₂-air mixture reaction catalyzed by Pt/C catalyst was examined. Experiments were carried out in a small-scale cylindrical vessel to investigate the effects of hydrogen volume fraction, catalyst mass, and inlet gas flow rate on the reaction process. The results revealed that the reaction temperature climbed as the hydrogen volume fraction increased, with a peak value achieved when the hydrogen volume fraction reached 35 vol%, and subsequently reduced as the hydrogen volume fraction increased further. The increase of the inlet gas flow rate also promoted the growth of reaction temperature. However, there was no significant linear relationship between the rise of catalyst mass and the change of reaction temperature.     

Pt=Pd separation modified Ti3C2TX MXene for hydrogen detection at room temperature

Hydrogen sensing with a fast response at room temperature is still a challenge. In this study, a novel Pt=Pd/Ti₃C₂T_X hydrogen sensor was prepared by a straightforward hydrothermal chemical reduction method. The Pt=Pd/Ti₃C₂T_X was characterized by X-ray diffraction, transmission electron microscope, and X-ray photoelectron spectroscopy. The experimental results showed that the response of the Pt=Pd/Ti₃C₂T_X sensor was 24.6% and the response/recovery time was 6/8 s in the case of 200 ppm hydrogen at room temperature. The Pt=Pd/Ti₃C₂T_X sensor could detect the hydrogen concentration as low as 1 ppm. Besides, the Pt=Pd/Ti₃C₂T_X sensor exhibited good linearity, long-term stability, good repeatability, and high selectivity. The Pt=Pd/Ti₃C₂T_X sensor has great potential in the field of hydrogen energy.     

Enhanced hydrogen production by the catalytic alkaline thermal gasification of cellulose with Ni/Fe dual-functional CaO based catalysts

A two-stage system involving alkaline thermal gasification of cellulose with Ca(OH)₂ sorbent and catalytic reforming with Ni/Fe dual-functional CaO based catalysts is proposed and applied to enhance H₂ production and in-situ CO₂ capture. The results show that the H₂ concentration is maximized at a considerably lower temperature (500 °C) than commercialized biomass gasification processes, reducing energy consumption. Sol-gel method is deemed better than impregnation method for its lower cost and higher-concentration H₂ production. Among the prepared catalysts, sol-NiCa catalyst exhibits the best performance in CO₂ absorption, resistance to carbon deposition, and cyclic stability, creating maximum H₂ concentration (79.22 vol%), H₂ yield (27.36 mmol g⁻¹ cellulose), and H₂ conversion (57.61%). Introduction of Ni rather than Fe on the CaO based catalyst promotes steam methane reforming at moderate temperature range of 400–600 °C, generating low contents of CH₄ (5.38 vol%), CO₂ (4.82 vol%), and CO (10.58 vol%).     

Photocatalytic production of hydrogen and methane from glycerol reforming over Pt/TiO2–Nb2O5

In this study, platinized mixed oxides (TiO₂–Nb₂O₅) were tested on photocatalytic hydrogen production from a glycerol solution under UV light. Different samples with different Ti:Nb ratios were prepared by using a simple method that simultaneously combined a physical mixture and a platinum photochemical reduction. This method led to improved physicochemical properties such as low band gap, better Pt nanoparticle distribution on the surface, and the formation of different Pt species. Niobia content was also found to be an important factor in determining the overall efficiency of the Pt–TiO₂–Nb₂O₅ photocatalyst in the glycerol reforming reaction. The photocatalytic results showed that Pt on TiO₂–Nb₂O₅ enhanced hydrogen production from the aqueous glycerol solution at a 5 wt% initial glycerol concentration. The influence of different operating conditions such as the catalyst dosage and initial glycerol concentration was also evaluated. The results indicated that the best hydrogen and methane production was equal to 6657 μmol/L and 194 μmol/L, respectively after 4 h of UV radiation using Pt/Ti:Nb (1:2) sample and with 3 g/L of catalyst dosage. Moreover, the role of water in photocatalytic hydrogen production was studied through photocatalytic activity tests in the presence of D₂O. The obtained results confirmed the role of water molecules on the photocatalytic production of hydrogen in an aqueous glycerol solution.     

Production of high purity hydrogen by sorption enhanced steam reforming of crude glycerol

Here we report effective production of pure hydrogen from crude glycerol by the one-stage sorption enhanced steam reforming (SESR) process. This process yielded H₂ up to 88% with a very high purity (99.7 vol%) at atmospheric pressure and at 550–600 °C with a steam/C = 3 in a fixed-bed reactor over a mixture of Ni/Co catalyst derived from hydrotalcite-like material (HT) and dolomite as CO₂ sorbent. The concentration of methane is lowest at 575 °C, while the CO concentration increases concurrently with increasing temperature from 525 to 600 °C. The high coking potential of glycerol and fatty acid methyl esters (C₁₇–C₁₉) resulted in the increased formation of coke, thus lower hydrogen yield. The reaction rates of methane reforming and water–gas shift reactions are much higher than the steam reforming of crude glycerol on Co–Ni catalysts. The high purity of hydrogen can be obtained even at low spatial times with low crude glycerol conversions. Our work reveals a great potential to directly convert biomass derived complex mixtures to the most clean energy carrier of hydrogen with high yield and purity.     

Toluene addition to turbulent H2/natural gas flames in bluff-body burners

A key challenge in the transition towards using hydrogen as an alternative carbon-free fuel is the reduced thermal radiation due to the absence of soot. A novel solution to this may be doping with highly sooting bio-oils. This study investigates the efficacy of toluene as a prevapourised dopant in turbulent pure hydrogen and blended hydrogen/natural gas flames as a means of improving soot loading and radiant heat transfer. All flames are stabilised on bluff-body burners to emulate the recirculation component of many industrial combustors. Total heat flux and illuminance increase non-linearly with toluene concentration for fuel blends and bluff-body diameters. By reducing the bluff-body diameter from 64 mm to 50 mm, a 20/80 (vol%) H₂/natural gas mixture produces a more radiative flame than a 10/90H₂/natural gas mixture in the smaller bluff-body. Opposed-flow flame simulations of soot precursors indicate that as strain rate increases, although overall soot precursor concentration decreases, a 20 vol% hydrogen mixture will produce more soot than a 10 vol% mixture. This suggests the addition of hydrogen up to 20 vol% may be beneficial for soot production in high strain environments.     

Photo-induced reforming of alcohols with improved hydrogen apparent quantum yield on TiO2 nanotubes loaded with ultra-small Pt nanoparticles

Photo-induced reforming of methanol, ethanol, glycerol and phenol at room temperature for hydrogen production was investigated with the use of ultra-small Pt nanoparticles (NPs) loaded on TiO₂ nanotubes (NTs). The Pt NPs with diameters between 1.1 and 1.3 nm were deposited on TiO₂ NTs by DC-magnetron sputtering (DC-MS) technique. The photocatalytic hydrogen rate achieved an optimum value for a loading of about 1 wt% of Pt. Apparent quantum yield for hydrogen generation was measured for methanol and ethanol water solutions reaching a maximum of 16% under irradiation with a wavelength of 313 nm in methanol/water solution (1/8 v/v). Pt NPs loaded on TiO₂ NTs represented also a true water splitting catalyst under UV irradiation and pure distilled water. DC-MS method appears to be a technologically simple, ecologically benign and potentially low-cost process for production of an efficient photocatalyst loaded with ultra-small NPs with precise size control.     

Hydrogen generation from sodium borohydride hydrolysis by multi-walled carbon nanotube supported platinum catalyst: A kinetic study

In this study, it is aimed to investigate hydrogen (H₂) generation from sodium borohydride (NaBH₄) hydrolysis by multi-walled carbon nanotube supported platinum catalyst (Pt/MWCNT) under various conditions (0–0.03 g Pt amount catalyst, 2.58–5.03 wt % NaBH₄, and 27–67 °C) in detail. For comparison, carbon supported platinum (Pt/C) commercial catalyst was used for H₂ generation experiments under the same conditions. The reaction rate of the experiments was described by a power law model which depends on the temperature of the reaction and concentrations of NaBH₄. Kinetic studies of both Pt/MWCNT and Pt/C catalysts were done and activation energies, which is the required minimum energy to overcome the energy barrier, were found as 27 kJ/mol and 36 kJ/mol, respectively. Pt/MWCNT catalyst is accelerated the reaction less than Pt/C catalyst while Pt/MWCNT is more efficient than Pt/C catalyst, they are approximately 98% and 95%, respectively. According to the results of experiments and the kinetic study, the reaction system based on NaBH₄ in the presence of Pt/MWCNT catalyst can be a potential hydrogen generation system for portable applications of proton exchange membrane fuel cell (PEMFC).     

Molybdenum disulfide decorated palm oil waste activated carbon as an efficient catalyst for hydrogen generation by sodium borohydride hydrolysis

Development of cost-effective catalyst material with enhanced activity for hydrogen generation is highly desirable for hydrogen powered portable applications. In this work, molybdenum disulfide (MoS₂) incorporated on palm oil waste activated carbon (POAC) was used as a novel catalyst for enhanced hydrogen production by sodium borohydride (NaBH₄) hydrolysis. Hydrothermally synthesized MoS₂/POAC catalyst composite was characterized by SEM, EDX, XRD, FTIR, Raman, TGA and Surface area analysis. Characterization studies revealed the uniform and complete synthesis of MoS₂ nanoparticles on the POAC surface with crystallite size of 18.2 nm. The catalyst composite showed enhancement in thermal stability and reduction in specific surface area as compared with POAC. Hydrogen generation investigations showed ideal weight ratio of composite catalyst as 10:1 (w/w of POAC: MoS₂) and optimal catalyst to feed weight ratio as 0.07. MoS₂/POAC catalyst with 10 wt% of POAC loading recorded the maximum catalytic activity of 1170.66 mL/g min with lower activation energy of 39.1 kJ/mol. The catalyst composite exhibited virtuous reusability with a 28% loss in activity for nine cycle regeneration run. Thus, MoS₂/POAC catalyst system is highly attractive for commercial applicability and is a potential candidate for enhanced hydrogen production through NaBH₄ hydrolysis.     

Efficient generation of hydrogen from biomass without carbon monoxide at room temperature – Formaldehyde to hydrogen catalyzed by Ag nanocrystals

In this paper, we present a new route for hydrogen generation from biomass at room temperature without any carbon monoxide over nano-metal-catalysts. It has been found that the Ag nanocrystals are highly efficient and stable catalysts for the CO-free hydrogen production from formaldehyde (HCHO), a model compound of biomass, at room temperature and at atmospheric pressure. By optimizing the structure and component of catalysts, reaction parameters such as temperature, catalyst amounts, oxygen, formaldehyde concentrations, and NaOH concentrations, the hydrogen generation rate has been maintained for hours without any decay. Furthermore, the apparent activation energy of the Ag catalyzed hydrogen production reaction is determined to be 11.8 kJ mol⁻¹, which was much lower than that of the literature results (65 kJ mol⁻¹) without catalyst. Because of its high hydrogen generation rate, hydrogen generation efficiency, lower activation energy, and the low cost, we speculate that this novel Ag catalyst based hydrogen generation reaction should be a promising candidate for providing hydrogen in PEMFCs at room temperature.     

Evaluation of catalyst activity for release of hydrogen from liquid organic hydrogen carriers

This contribution investigate the effect of parameters for production of hydrogen by catalytic dehydrogenation of perhydrodibenzyltoluene (H18-DBT). The sensitivity of the dehydrogenation reaction to temperature (290–320 °C) is justified by an increase in degree of dehydrogenation (DoD) from 40 to 90% when using 1 wt % Pt/Al₂O₃ catalyst. However, the increase in temperature increases the hydrogen production rate and decreases the hydrogen purity by increasing the formation of by-products. In addition, the DoD of 96% is obtained when 2 wt % Pt/Al₂O₃ is used at 320 °C. The DoD obtained for Pd, Pt, and Pt–Pd catalysts is 11, 82 and 6%, respectively. Therefore, Pd is not a metal of choice for dehydrogenation of H18-DBT, in both monometallic and bimetallic system. The ab-initio density functional theory (DFT) calculations are consistent with this observation. Furthermore, dehydrogenation of H18-DBT followed 1st order reaction kinetics and the activation energies for 1 wt % Pt/Al₂O₃, 1 wt % Pd/Al₂O₃ and 1:1 wt % Pt–Pd/Al₂O₃ catalysts are: 205, 84 and 66 kJ/mol, respectively.