Mol H2 Research Articles

Eco‐Friendly Preparation of Pectin‐Stabilized Ruthenium Catalyst for Hydrogen Generation from Sodium Borohydride Hydrolysis

AbstractIn this study, we report that pectin‐supported ruthenium nanoparticles (pectin@Ru0) can be easily prepared at room temperature by a simple and effective method and that they exhibit outstanding catalytic activity in the hydrolysis of sodium borohydride (NaBH4). The structure, oxidation state, morphology, and thermal studies were analyzed using XRD, XPS, SEM, TEM and TGA analysis. The kinetic performance of pectin@Ru0 biocatalyst was evaluated depending on ruthenium loading, NaBH4 concentration, NaOH concentration, temperature, reusability and storage. The pectin@Ru0 biocatalyst containing 2 wt.% Ru0 metal catalyzed the hydrolysis of 50 mM NaBH4+1 wt.% NaOH with 100 % yield. The activation energy (Ea) and the TOF values of the reaction was estimated as 54.7 kJ mol−1 and 53.1 mol H2 (mol Ru0 min) −1 at 30 °C and this is consistent with other previously reported catalysts, making it a remarkable result in comparison. Reusability and catalytic life studies reported that pectin@Ru0 biocatalyst is also highly active and relatively long‐lived catalyst in the hydrolysis of NaBH4 in a slightly basic solution.

Magnetite Fe3O4 nanoparticles impregnated on Chlorella vulgaris microalgae: Its role in obtaining hydrogen from the sodium borohydride-hydrolysis

Recently, the single-celled green freshwater microalgae species “Chlorella vulgaris” has attracted the attention of researchers due to its different usage areas. In particular, research focuses on the technology of obtaining bio‑hydrogen with various techniques. This research involves, for the first time, the use of the microalga Chlorella vulgaris as a bio-supporting material for magnetite Fe3O4 nanoparticles (Fe3O4NPs@Chlorella vulgaris) and the production of hydrogen through catalytic hydrolysis of NaBH4 (sodium borohydride, SB) in the presence of the resulting magnetite nanoparticles. Here, detailed kinetic studies were carried out during the SB-hydrolysis by taking magnetite Fe3O4NPs@Chlorella vulgaris and SB in varying amounts and at varying temperatures, and the activation energy and lifetime of magnetite Fe3O4NPs@Chlorella vulgaris was found to be 23.49 kJ mol−1 and 93,280 mol H2 (mol Fe3O4)−1, respectively. No change in the chemical and physical structure of the biocatalyst was observed during the hydrolysis of SB, so only detailed characterization of microalgae and magnetite Fe3O4NPs@Chlorella vulgaris was performed, and the particle size of the catalyst was calculated as 10.19 ± 2.17 nm. The results showed that these Fe3O4NPs@Chlorella vulgaris, which can be easily separated magnetically and have high catalytic activity, are a “clean” and quite surprising catalyst in terms of hydrogen production.

1-Dimensional metal Nitride-Supported platinum nanoclusters for Low-Temperature hydrogen production from formic acid

Formic acid is widely recognized as a suitable liquid hydrogen carrier for linking renewable energies toward various economic sectors. Designing efficient and stable heterogeneous catalysts for low-temperature hydrogen generation from formic acid is vital for this topic. In this study, a rational hierarchical architecture is explored by assembling Pt nanoclusters with 1-dimensional (1D) GaN nanowires. The catalytic architecture describes a considerable hydrogen production activity of 54.89 mmol·gcat−1·h−1 with a nearly 100 % selectivity and a turnover frequency (TOFPt) of 505.7 h−1 under near ambient condition, enables the achievement of a high turnover number of 306,981 mol H2 per mole Pt over 200 h of long-term operation. Through comprehensive mechanistic studies, it is unraveled that the synergistic effect between Pt nanoclusters and GaN significantly reduces the energy barrier for the formation of the key HCOO* intermediate from formic acid dehydrogenation whereas significantly increase the energy barrier of HCOOH → HCO* + *OH. It thus simultaneously contributes to improving the activity and selectivity of formic acid decomposition toward H2. This study proposes a promising strategy for hydrogen generation from formic acid at low temperatures, which is critical for achieving carbon neutrality by coordinating industrial waste heat with renewable energies via liquid hydrogen carriers.

Composition of gasolinefractions of Kumkol oil and improvement of theiroperational properties

The physicochemical properties of gasoline fractions of paraffinic oil from the Kumkol field have been investigated and the distinctive features of the individual hydrocarbon composition of the straight-run gasoline fraction and catalytic reforming gasoline have been established. The wide straight-run gasoline fraction (62-180°C) of Kumkol oil was subjected to preliminary hydrotreating at an industrial unit that is part of the catalytic reforming unit using S-12T and GO70 catalysts at a process temperature of 315 – 343°C, a pressure in the reactor of 21 – 27 atm, a volume feed rate of 6.4 – 9.4 h-1, with the circulation of HCG (Hydrogen-containing gas) «on the duct». Conditions under which catalytic reforming was carried out: temperature in the reaction zone – 470 ÷ 500°C, pressure – 28 kgf/cm2 , volumetric feed rate of raw materials – 1.5 h-1, gas circulation – 5.9 mol H2 / mol of raw materials. It has been established that in the process of reforming, as a result of isomerization of n-paraffins and dehydrogenation of cylanes, isoparaffin and aromatic hydrocarbons are intensively formed in the composition of reformant, and thereby the octane number of reforming gasoline is sharply increased. Gasoline obtained in the process of catalytic reforming from a narrow fraction of Kuikol oil meets the requirements for commercial, high-octane grades of motor fuel in all quality indicators. A significant synergistic effect has been established with the combined action of a two-component mixture compared to that for individual additives: a small concentration of the additive Hightech (manganese-containing) 18 mg/l and oxygen-containing AHA (ash-free high-octane additive) increases the octane number M.M. (motor method) by 3.3 points and according to R.M. (research method) by 5.3 points, and when introducing the additive Hitech 18 mg/l in a mixture with N-methylaniline, the increase in the O.N. (octane number) for M.M. was 4.4 units, and for R.M. (research method) – 6.

Techno-economic assessment of bio-hythane upgrading processes based on ionic liquids

Hythane, the blending of hydrogen (H2) and methane (CH4), is attracting attention as it could accelerate the H2 economy. H2 and CH4 can be extracted from organic material by fermentation and anaerobic digestion, respectively, but this alternative bio-hythane also contains carbon dioxide (CO2) that must be removed. This work addresses the use of Aprotic N‑Heterocyclic Anion-based ionic liquids (AHA-ILs) for bio-hythane upgrading. Three AHA-ILs ([P2228][2-CNPyr], [P2228][3-IPyra], and [P2228][4-BrIm]) were evaluated at process scale by conducting rate-based COSMO-based/Aspen Plus simulations of the upgrading processes. A wide range of operating conditions were screened by modifying key process variables such as the absorption pressure and the desorption temperature, and the bio-hythane composition. Energy and AHA-IL consumptions were analyzed together with variable operating cost (VOC). Energy demand and VOC were used to identify the Pareto optimal for each case study using a Python code. In addition, a detailed economic study was performed for the best three systems. The proposed processes are very versatile and are capable of handling bio-hythane of different compositions, being 10 %mol H2, 60 %mol CH4, and 30 %mol CO2 the most suitable for better process performance. For this case, the energy demand is about 0.51–0.56 kWh/Nm3 and VOC is about 1 cent. $/Nm3. The AHA-IL [P2228][3-IPyra] exhibited the best results for both variables. The energy requirement is in line with the minimum energy required for amine scrubbing technology, while VOC can be reduced by up to 17–48 % compared with electricity-intensive water scrubbing, pressure swing adsorption or membranes. Although higher investment is necessary, the assessed bio-hythane upgrading processes have the potential to operate around 0.1 $/Nm3, with VOC contributing about 8 % to the total cost.

Evaluation of hydrogen storage performance of Ti0.25Zr0.25V0.15Nb0.15Ta0.2 high-entropy alloy using calorimetric technique

The features of phase transformations during interaction of BCC-type Ti0.25Zr0.25V0.15Nb0.15Ta0.2 high-entropy alloy (HEA) with hydrogen and the accompanying thermal effects have been examined using the Tian-Calvet calorimetric technique. The alloy was produced by the pendent drop melt extraction method in the form of microfibers and then coated with a thin layer of palladium to eliminate the preliminary high-temperature activation and enable first hydrogenation at room temperature. Two reaction stages were distinguished on the measured heat emission curves. Using XRD data, these stages were attributed to the formation of a BCC-type hydrogen solid solution and a phase transition to FCC-type dihydride phase. Recorded values of the reaction enthalpy decrease in absolute terms from 145 kJ/mol H2 (dilute solid solution) to 73–77 kJ/mol H2 (BCC→FCC) and to 20 kJ/mol H2 (H solution in FCC dihydride). The overall heat emission of the entire process as a whole is 110 kJ/ mol H2. The course of the dehydrogenation process depends strongly on the applied temperature and at 493 K results in the formation of a BCT-type monohydride, which was not detected during hydrogenation. The detailed calorimetric data obtained here significantly change the previously existing ideas about thermal effects during this type HEAs hydrogenation, based on calculations using the Van't-Hoff equation. The reported findings are of special importance for various hydrogen related applications of HEAs

Unveiling Highly Sensitive Active Site in Atomically Dispersed Gold Catalysts for Enhanced Ethanol Dehydrogenation

AbstractDeveloping a desirable ethanol dehydrogenation process necessitates a highly efficient and selective catalyst with low cost. Herein, we show that the “complex active site” consisting of atomically dispersed Au atoms with the neighboring oxygen vacancies (Vo) and undercoordinated cation on oxide supports can be prepared and display unique catalytic properties for ethanol dehydrogenation. The “complex active site” Au−Vo−Zr3+ on Au1/ZrO2 exhibits the highest H2 production rate, with above 37,964 mol H2 per mol Au per hour (385 g H2 h−1) at 350 °C, which is 3.32, 2.94 and 15.0 times higher than Au1/CeO2, Au1/TiO2, and Au1/Al2O3, respectively. Combining experimental and theoretical studies, we demonstrate the structural sensitivity of these complex sites by assessing their selectivity and activity in ethanol dehydrogenation. Our study sheds new light on the design and development of cost‐effective and highly efficient catalysts for ethanol dehydrogenation. Fundamentally, atomic‐level catalyst design by colocalizing catalytically active metal atoms forming a structure‐sensitive “complex site”, is a crucial way to advance from heterogeneous catalysis to molecular catalysis. Our study advanced the understanding of the structure sensitivity of the active site in atomically dispersed catalysts.

Unveiling Highly Sensitive Active Site in Atomically Dispersed Gold Catalysts for Enhanced Ethanol Dehydrogenation.

Developing a desirable ethanol dehydrogenation process necessitates a highly efficient and selective catalyst with low cost. Herein, we show that the "complex active site" consisting of atomically dispersed Au atoms with the neighboring oxygen vacancies (Vo) and undercoordinated cation on oxide supports can be prepared and display unique catalytic properties for ethanol dehydrogenation. The "complex active site" Au-Vo-Zr3+ on Au1/ZrO2 exhibits the highest H2 production rate, with above 37,964 mol H2 per mol Au per hour (385 g H2 h-1) at 350 °C, which is 3.32, 2.94 and 15.0 times higher than Au1/CeO2, Au1/TiO2, and Au1/Al2O3, respectively. Combining experimental and theoretical studies, we demonstrate the structural sensitivity of these complex sites by assessing their selectivity and activity in ethanol dehydrogenation. Our study sheds new light on the design and development of cost-effective and highly efficient catalysts for ethanol dehydrogenation. Fundamentally, atomic-level catalyst design by colocalizing catalytically active metal atoms forming a structure-sensitive "complex site", is a crucial way to advance from heterogeneous catalysis to molecular catalysis. Our study advanced the understanding of the structure sensitivity of the active site in atomically dispersed catalysts.

Understanding the impact of support materials on CoFe2O4 catalyst performance for hydrogen fuel and nanocarbon production via methane decomposition

This study focuses on assessing the performance and durability of three distinct catalysts, namely CoFe2O4/MgO and CoFe2O4/TiO2 and CoFe2O4/Al2O3 in the methane decomposition process. These catalysts were synthesized using a co-precipitation impregnation route. Their catalytic activity of methane decomposition was examined in a fixed-bed reactor at a temperature of 800 °C under atmospheric pressure. Various appropriate analytical techniques were employed to explore the physicochemical characteristics of both the fresh and spent catalysts. The SEM images, XRD and H2-TPR results of fresh catalysts revealed strong dependence on the support type. The XPS results confirm the presence CoFe2O4 species on the surface of supports. The CoFe2O4/MgO catalyst has a higher inversion degree compared with other catalysts as confirmed from Raman results. The methane conversions at the end of the reaction time (300 min) were found to be 66 %, 34 % and 2.48 %, while the rates of hydrogen formation corresponding to these methane conversions are 134.73 × 10−5, 68.25 × 10−5 and 8.80 × 10−5 mol H2 g−1 min−1 for CoFe2O4/MgO and CoFe2O4/TiO2 and CoFe2O4/Al2O3 catalysts, respectively. SEM images verified the existence of filamentous carbon on the surface of the spent CoFe2O4/MgO catalyst, whereas the spent CoFe2O4/TiO2 catalyst showed a mix of carbon chunks and filaments and fluffy carbon over the CoFe2O4/Al2O3 catalyst. Ultimately, the quantity of deposited carbon was significantly associated with catalytic activity, as they were 56, 46 and 4 wt% for the spent CoFe2O4/MgO, CoFe2O4/TiO2 and CoFe2O4/Al2O3 catalysts, respectively.

Deciphering the influence of support in the performance of NiFe2O4 catalyst for the production of hydrogen fuel and nanocarbon by methane decomposition

Wet chemical synthesis route was used to synthesis nickel ferrite (NiFe2O4) nanoparticle. Later on the synthesized NiFe2O4 were supported on the surface of three traditional supports such as Al2O3, MgO and TiO2 to get NiFe2O4/Al2O3, NiFe2O4/TiO2 and NiFe2O4/MgO catalysts. The activity profile of each catalyst was evaluated in a fixed-bed reactor for direct methane decomposition at 800 °C. For both fresh and spent catalysts, many characterization techniques have been employed mainly XRD, FESEM, HRTEM, Raman spectroscopy, TGA, and nitrogen adsorption-desorption isotherm. X-ray powder diffraction studies revealed that all synthesized catalysts have a cubic spinel crystal structure. The XRD confirm the presence of NiFe2O4 particles in the component of fresh NiFe2O4/MgO, NiFe2O4/TiO2 and NiFe2O4/Al2O3 catalysts. Temperature Program Reduction (TPR) unveiled the presence of Ni oxides and Fe oxides by displaying reduction peaks in their respective temperature regions. The N2 adsorption-desorption isotherms of the fresh all catalysts reveal that these catalysts have a mesoporous structure. Activity data concluded NiFe2O4/MgO to be the most active catalysts among the tested catalysts methane conversion magnitude of 41.13 % and H2 formation rate of 84.40 × 10−5 mol H2 g−1 min−1. On the other hand, the H2 formation rate drastically declined and very poor activity of both NiFe2O4/TiO2 and NiFe2O4/Al2O3 catalysts was observed in the current work. XRD patterns, FESEM images and TGA analysis of spent NiFe2O4/MgO catalyst shown the filamentous carbon formation which secondarily confirm its higher activity, while its absence in catalysts of NiFe2O4/TiO2 and NiFe2O4/Al2O3. TGA analysis of the carbon deposited on the NiFe2O4/MgO catalyst showed that the amount of carbon was approximately 64 wt%. It was suggested that the formation of nickel-iron carbide revealed by XRD studies of spent catalysts may be the factor related to their poor activity while discussing the structure-activity relationship. Likewise, the higher degree of dispersion related to NiFe2O4/MgO as displayed by XRD, FESEM and TPR investigations, played a vital role in accelerating the rate of hydrogen formation.

Oxide coated nickel powder as support for platinum(0) nanoparticles: Magnetically separable catalysts for hydrogen generation from the hydrolysis of ammonia borane

We report the development of a novel method for the preparation of magnetically separable platinum nanoparticles. Magnetic nickel nanopowder is initially synthesized in a radiofrequency plasma reactor where in-line passivation was carried out with oxygen gas, resulting in the formation of nickel oxidecoated nickel particles. Following this, platinum nanoparticles are deposited onto the surface of the oxidecoated nickel nanopowder, forming Pt0/Ni@NiO nanocatalysts for the hydrolytic dehydrogenation of ammonia borane. The Pt0/Ni@NiO nanoparticles, containing 0.24 % wt. Pt, exhibit remarkable catalytic activity in the hydrolytic dehydrogenation of ammonia borane, with a turnover frequency of 468 (mol H2)×(mol Pt)−1×min−1 for releasing 3 equivalent H2 gas per mole of ammonia borane from its hydrolysis at 25 ºC. This heightened catalytic activity of Pt0/Ni@NiO nanoparticles is attributed to the favorable metal-support interaction between the platinum(0) nanoparticles and oxide surface, namely the bonding of platinum to the oxide surface, as elucidated by the XPS analysis. More importantly, Pt0/Ni@NiO nanoparticles can be separated from the reaction solution by using an external magnet.

Investigation of the catalytic activity of Ag(0) nanoparticles supported into anionic hydrogel networks for hydrogen production process

In the presented study, the hydrogen production from the hydrolysis of the morpholine-borane (MB) with hydrogel supported Ag(0) nanoparticle catalyst system was reported. For this purpose, nanosized p(sulfopropyl acrylate potassium salt-co-itaconic acid)@Ag composite material, (p-SIH@Ag), was prepared and used as catalyst. In this study, the effects of base, catalyst amount, MB substrate concentration and temperature were investigated for the MB hydrolysis reaction. p-SIH@Ag catalyzed MB hydrolysis reaction at 30 °C, the activation energy (Ea) was determined as 24.3 kjmol−1 and the turn over frequency (TOF) as 37.52 mol H2(mol Ag(0).h)−1. In reusability studies, the catalyst preserved 72% of its activity even after the 5th catalytic cycle despite the sensitivity of Ag metal to oxidation. Our study is the first in the literature to use hydrogel supported Ag metal catalyst system in hydrogen production via MB hydrolysis.

Air-Promoted Light-Driven Hydrogen Production from Bioethanol over Core/Shell Cr2O3@GaN Nanoarchitecture.

Light-driven hydrogen production from biomass derivatives offers a path towards carbon neutrality. It is often however operated with the limitations of sluggish kinetics and severe coking. Herein, a disruptive air-promoted strategy is explored for efficient and durable light-driven hydrogen production from ethanol over a core/shell Cr2O3@GaN nanoarchitecture. The correlative computational and experimental investigations show ethanol is energetically favorable to be adsorbed on the Cr2O3@GaN interface, followed by dehydrogenation toward acetaldehyde and protons by photoexcited holes. The released protons are then consumed for H2 evolution by photogenerated electrons. Afterward, O2 can be evolved into active oxygen species and promote the deprotonation and C-C cleavage of the key C2 intermediate, thus significantly lowering the reaction energy barrier of hydrogen evolution and removing the carbon residual with inhibited overoxidation. Consequently, hydrogen is produced at a high rate of 76.9 mole H2 per gram Cr2O3@GaN per hour by only feeding ethanol, air, and light, leading to the achievement of a turnover number of 266,943,000 mole H2 per mole Cr2O3 over a long-term operation of 180 hours. Notably, an unprecedented light-to-hydrogen efficiency of 17.6 % is achieved under concentrated light illumination. The simultaneous generation of aldehyde from ethanol dehydrogenation enables the process more economically promising.

Air‐Promoted Light‐Driven Hydrogen Production from Bioethanol over Core/Shell Cr2O3@GaN Nanoarchitecture

AbstractLight‐driven hydrogen production from biomass derivatives offers a path towards carbon neutrality. It is often however operated with the limitations of sluggish kinetics and severe coking. Herein, a disruptive air‐promoted strategy is explored for efficient and durable light‐driven hydrogen production from ethanol over a core/shell Cr2O3@GaN nanoarchitecture. The correlative computational and experimental investigations show ethanol is energetically favorable to be adsorbed on the Cr2O3@GaN interface, followed by dehydrogenation toward acetaldehyde and protons by photoexcited holes. The released protons are then consumed for H2 evolution by photogenerated electrons. Afterward, O2 can be evolved into active oxygen species and promote the deprotonation and C−C cleavage of the key C2 intermediate, thus significantly lowering the reaction energy barrier of hydrogen evolution and removing the carbon residual with inhibited overoxidation. Consequently, hydrogen is produced at a high rate of 76.9 mole H2 per gram Cr2O3@GaN per hour by only feeding ethanol, air, and light, leading to the achievement of a turnover number of 266,943,000 mole H2 per mole Cr2O3 over a long‐term operation of 180 hours. Notably, an unprecedented light‐to‐hydrogen efficiency of 17.6 % is achieved under concentrated light illumination. The simultaneous generation of aldehyde from ethanol dehydrogenation enables the process more economically promising.

Optimization of hydrogen purification from biomass‐derived syngas via water gas shift reaction integrated with vacuum pressure swing adsorption for energy storage

AbstractBiomass is one of the promising sources to produce green H2, which can be considered an energy storage medium. To produce high‐purity H2 from biomass‐derived syngas, this study implemented a two‐stage H2 purification process. In the first stage, a water gas shift reaction (WGSR) was performed to enhance the H2 concentration in the syngas. The Taguchi method was employed to analyze the influence of the operating conditions and maximize the H2 concentration in the water gas shift reaction product. The results suggested that reaction temperature is a more dominant factor for enhancing the H2 concentration than the molar steam/carbon monoxide (S/CO) ratio. In the second stage, vacuum pressure swing adsorption was employed to obtain the high‐concentration H2 using the product from the water gas shift reaction having the optimum H2 concentration. Using the adsorption pressure as the primary parameter, it was found that high H2 purity and recovery could be obtained from vacuum pressure swing adsorption operated at low adsorption pressures. Based on this study's results, the vacuum pressure swing adsorption unit's best outcome occurs during an adsorption pressure of 2 kg·cm−2 and a flow rate of 17 L·min−1. Under these conditions, 93.61% H2 purity, 31.63% H2 recovery, 4.86 mol H2·(kgads·h)−1 productivity, and 448.14 kJ·(kg H2)−1 energy consumption are obtained.

Exploration of novel phenyl mercury tetrazole‐thione complexes: Characterization and investigating the impact of diamine ligands on enhanced hydrogen storage

AbstractTen mixed‐ligand phenyl mercury(II) complexes containing 1‐methyl‐1H‐tetrazole‐5‐thiol (HmtzS) (1) and phosphine or amine ligands. These complexes fall into two groups: [PhHg(mtzS){Ph2P(CH2)PPh2}]2 (2) and [PhHg(mtzS){Ph2P(CH2)nPPh2}] (3‐6), where n varies, and [PhHg(mtzS)(diamine)] (8‐10), with diamine choices being 2,2′‐bipyridyl (Bipy, 8), 1,10‐phenathroline (Phen, 9), or ethylenediamine (en, 10). These complexes were synthesized with moderate to high yields and characterized using various techniques. Characterization data revealed that the mtzS− ligand coordinates as a monodentate ligand through the thiolate sulfur atom in all complexes, adopting a tetrahedral geometry around the Hg(II) center. Furthermore, complexes [PhHg(mtzS)] (1) and its diamine derivatives (8‐10) were assessed for hydrogen storage at 77 K using the VTI method. Results demonstrated that the incorporation of diamines improves hydrogen storage capacity at low pressure. The precursor stored (1) 2.3 wt.% at 80 bar, while the other complexes showed storage capacities ranging from 2.9 to 3.86 wt.% at pressures of 45‐60 bar. Thermodynamic properties of the [PhHg(mtzS)(Bipy)] complex was calculated at three different temperatures. The results prove that the entropy was equal to 0.50543599 J/mol H2. K while the enthalpy equal to 0.0942638 KJ/(mol H2).

Palladium (0) nanoparticles distributed on lanthanum (III) oxide as an effective catalyst for the methanolysis of hydrazine-borane to produce hydrogen.

Pd (0) nanoparticles (NPs) distributed on lanthanum (III) oxide were ex situ generated from the reduction of Pd2+ ions using NaBH4 as reducing agent. The Pd/La2O3 displayed good catalytic activity in H2(g) releasing from the hydrazine-borane (HB) methanolysis reaction and it was identified by advanced techniques. Pd/La2O3 was found to be an active catalyst procuring three equiv. H2(g) per mole of HB. The results from TEM images represent the formation of Pd (0) NPs with an average particle size of 1.94 ± 0.1 nm on the surface of La2O3. Moreover, Pd/La2O3 with various Pd loadings were prepared and tested as catalyst in the methanolysis reaction to find the optimum metal loading on La2O3 support. The highest H2 formation rate was achieved with 3.0 wt% Pd. Pd/La2O3 catalyst exhibited a turnover frequency (TOF) value of 24.4 mol H2 mol Pd-1 min-1 in the reaction conditions. Additionally, the effect of different catalyst concentrations and temperatures on the reaction kinetics for the methanolysis of HB catalyzed by Pd/La2O3.

Probing efficient microbial CO2 utilisation through metabolic and process modelling.

Acetogenic gas fermentation is increasingly studied as a promising technology to upcycle carbon-rich waste gasses. Currently the product range is limited, and production yields, rates and titres for a number of interesting products do not allow for economically viable processes. By pairing process modelling and host-agnostic metabolic modelling, we compare fermentation conditions and various products to optimise the processes. The models were then used in a simulation of an industrial-scale bubble column reactor. We find that increased temperatures favour gas transfer rates, particularly for the valuable and limiting H2 , while furthermore predicting an optimal feed composition of 9:1 mol H2 to mol CO2 . Metabolically, the increased non-growth associated maintenance requirements of thermophiles favours the formation of catabolic products. To assess the expansion of the product portfolio beyond acetate, both a product volatility analysis and a metabolic pathway model were implemented. In-situ recovery of volatile products is shown to be within range for acetone but challenging due to the extensive evaporation of water, while the direct production of more valuable compounds by acetogens is metabolically unfavourable compared to acetate and ethanol. We discuss alternative approaches to overcome these challenges to utilise acetogenic CO2 fixation to produce a wider range of carbon negative chemicals.

Ni-doped NbC films for remarkably enhancing hydrogen permeation performance of NbC/V composite membranes

Niobium carbide (NbC) membranes have been shown to be an effective catalytic membrane for hydrogen dissociation and desorption. Here, magnetron sputtering method was applied to dope Ni in NbC films to improve the catalytic properties. It is found that the Ni doping largely affects the surface microstructure and electronic structure of the NbC films, which in turn affects the hydrogen permeation performance of the NbC/V composite membranes. By density functional theory (DFT) calculations, it is known that the doping of Ni can modulate the internal electronic structure of NbC, such as d-band center and bader charge, thus improving the catalytic properties of the NbC films. Typically, under the optimal preparation conditions, the hydrogen permeability of the Ni-doped NbC/V composite membranes was 2.59 × 10−8 mol H2 m−1 s−1 Pa−0.5，at 500 °C, which is higher than that of pure Pd under the same conditions. These findings open up a new way towards the improvement of the catalytic properties for the hydrogen separation membrane materials.

Unravelling the kinetics, isotherms, thermodynamics, and mass transfer behaviours of Zeolite Socony Mobil - 5 in removing hydrogen sulphide resulting from a dark fermentative biohydrogen production process.

Research into the speciation of sulfur and hydrogen molecules produced through the complex process of thermophilic dark fermentation has been conducted. Detailed surface studies of solid-gas systems using real biogas (biohydrogen) streams have unveiled the mechanisms and specific interactions between these gases and the physicochemical properties of a zeolite as an adsorbent. These findings highlight the potential of zeolites to effectively capture and interact with these molecules. In this study, the hydrogen sulphide removal analysis was conducted using 0.8 g of the adsorbent and at various reaction temperatures (25-125 °C), a flow rate of 100 mL min-1, and an initial concentration of approximately 5000 ppm hydrogen sulphide. The reaction temperature has been observed to be an essential parameter of Zeolite Socony Mobil - 5 adsorption capacity. The optimum adsorption capacity attains a maximum value of 0.00890 mg g-1 at an optimal temperature of 25 °C. The formation of sulphur species resulting from the hydrogen sulphide adsorption on the zeolite determines the kinetics, thermodynamics, and mass transfer behaviours of Zeolite Socony Mobil - 5 in hydrogen sulphide removal and Zeolite Socony Mobil - 5 is found to improve the quality of biohydrogen produced in thermophilic environments. Biohydrogen (raw gas) yield was enhanced from 2.48 mol H2 mol-1 hexose consumed before adsorption to 2.59 mol H2 mol-1 hexose consumed after adsorption at a temperature of 25 °C. The Avrami kinetic model was fitted for hydrogen sulphide removal on Zeolite Socony Mobil - 5. The process is explained well and fitted using the Temkin isotherm model and the investigation into thermodynamics reveals that the adsorption behaviour is exothermic and non-spontaneous. Furthermore, the gas molecule's freedom of movement becomes random. The adsorption phase is restricted by intra-particle diffusion followed by film diffusion during the transfer of hydrogen sulphide into the pores of Zeolite Socony Mobil - 5 prior to adsorption on its active sites. The utilisation of Zeolite Socony Mobil - 5 for hydrogen sulphide removal offers the benefit of reducing environmental contamination and exhibiting significant applications in industrial operations.