The role of oxygen vacancies in the CO2 methanation employing Ni/ZrO2 doped with Ca

The Ni/ZrO₂ catalyst doped with Ca and Ni/ZrO₂ were employed in the CO₂ methanation, a reaction which will possibly be used for storing intermittent energy in the future. The catalysts were characterized by X-ray photoelectron spectroscopy (XPS, reduction in situ), X-ray diffraction (XRD, reduction in situ and Rietveld refinement), electron paramagnetic resonance (EPR), temperature-programmed surface reaction, cyclohexane dehydrogenation model reaction, temperature-programmed desorption of CO₂ and chemical analysis. The catalytic behavior of these catalysts in the CO₂ methanation was analyzed employing a conventional catalytic test. Adding Ca to Ni/ZrO₂, the metallic surface area did not change whereas the CO₂ consumption rate almost tripled. The XRD, XPS and EPR analyses showed that Ca⁺² but also some Ni²⁺ are on the ZrO₂ surface lattice of the Ni/CaZrO₂ catalyst. These cations form pairs which are composed of oxygen vacancies and coordinatively unsaturated sites (cus). By increasing the number of these pairs, the CO₂ methanation rate increases. Moreover, the number of active sites of the CO₂ methanation rate limiting step (CO and/or formate species decomposition, rls) is enhanced as well, showing that the rls occurs on the vacancies-cus sites pairs.     

Synergistic effect of titanium oxide underlayer and interlayer on zirconium-doped zinc ferrite photoanode for photoelectrochemical water splitting

Here, we report the synergistic effect of dual TiO₂ layers to enhance the PEC performance of Zirconium-doped zinc ferrite (ZZFO) photoanode by improving the charge carrier density and suppressing the photogenerated charge recombination. The TiO₂ underlayer works as a blocking layer to remarkably suppress the back-injection of electrons from the fluorine-doped tin oxide (FTO) leading to reducing the bulk charge recombination. While interlayer TiO₂ improves the bulk charge transfer property of ZZFO photoanodes. The optimal TiO₂ double-layer modified ZZFO photoanode exhibits an enhanced photocurrent of 0.435 mA/cm² at 1.23 V vs. reversible hydrogen electrode (RHE), which is 2.5 times higher than that of the ZZFO photoanode. The effect of each layer was deeply investigated by electrochemical impedance spectroscopy (EIS), intensity-modulated photocurrent spectroscopy (IMPS) and time-resolved photoluminescence studies (TRPL) with the aim of gaining a clear picture of the interface modifications and their impact on the efficiency of the ZZFO photoanode.     

Enhanced hydrogen storage performance of Cu3(BTC)2 in situ inserted with few-layer silicon-based nanosheets

Silicon-based nanosheets (SNS) were synthesised via a mild (60 °C) and time-saving (8 h) modified topochemical method. Then, Cu₃(BTC)₂ and SNS@Cu₃(BTC)₂ were successfully synthesised by microwave irradiation, and their characteristics and hydrogen storage performance were analysed by multiple techniques. The accordion-like SNS exhibited void spaces, a unique low buckled structure, and ultrathin, almost transparent, loosely stacked layers with a high specific surface area (362 m²/g). After in-situ synthesis with Cu₃(BTC)₂, the SNS compound achieved a high specific surface area (1526 m²/g), outstanding hydrogen storage performance (5.6 wt%), and a desirable hydrogen diffusion coefficient (10^?7). Thus, SNS doping improved the hydrogen storage performance of Cu₃(BTC)₂ by 64% through electron transfer reactions with Cu enabled by the unique composite nanostructure of SNS@Cu₃(BTC)₂. This study presents a promising method of synthesising SNS and porous composite materials for hydrogen storage.     

Natural aloe vera derived Pt supported N-doped porous carbon: A highly durable cathode catalyst of PEM fuel cell

Evolution of highly durable electrocatalyst for oxygen reduction reaction (ORR) is the most critical barrier in commercializing polymer electrolyte membrane fuel cell (PEMFC). In this work, Pt deposited N-doped mesoporous carbon derived from Aloe Vera is developed as an efficient and robust electro catalyst for ORR. Due to its high mesoporous nature, the aloe vera derived carbon (AVC) play a very vital role in supporting Pt nanoparticles (NPs) with N-doping. After doping N into AVC, more defects are created which facilitates uniform distribution of Pt NPs leading to more active sites towards ORR. Pt/N-AVC shows excellent ORR activity when compared with commercial Pt/C and showing a half wave potential (E_1/2–0.87 V Vs. RHE) and reduction potential (E_red ~ 0.72 V Vs. RHE) towards ORR. Even after 30,000 potential cycles, Pt/N-AVC shows in its E_1/2 only ~5 mV negative shift and lesser agglomeration of Pt NPs is seen in the catalyst. In membrane electrode assembly (MEA) fabrication, Pt/N-AVC as a cathode catalyst in a PEMFC fixture and performance were studied. The Pt/N-AVC shows good performance, which proves the potential application of this naturally available bio derived carbon, which serves as an excellent high durable support material in PEMFC. All these features show that the Pt/N-AVC is the most stable, efficient and suitable candidate for ORR catalyst.     

Nickel-loaded red mud catalyst for steam gasification of bamboo sawdust to produce hydrogen-rich syngas

Ni/red mud (RM) catalysts were prepared by wet impregnation and used in the catalytic steam gasification of bamboo sawdust (BS) to produce hydrogen-rich syngas. The system was optimized in terms of the amount of added nickel (10%), reaction temperature (800 °C), and catalyst placement (separately behind the BS). The maximum H₂ yield was 17.3% higher than that using pure RM catalyst and 43.8% higher than that of BS gasification alone, and the H₂/CO ratio in the syngas reached 7.82. This Ni/RM catalyst also retained good activity after six cycles in a double-stage fixed bed reactor. Analysis using X-ray fluorescence, X-ray diffraction, scanning electron microscopy-energy dispersive spectroscopy, and other methods revealed that the interaction of Ni, Fe, and Mg in Ni/RM produced bimetallic compounds containing active sites, such as NiFe₂O₄, MgNiO₂, and NiO. This explains the good catalytic performance in the tar conversion during the gasification process.     

Facile modified polyol synthesis of FeCo nanoparticles with oxyhydroxide surface layer as efficient oxygen evolution reaction electrocatalysts

The oxygen evolution reaction (OER) at anode requires high overpotential and is still challenging. The metallic core-oxyhydroxide layer structure is an efficient method to lower an overpotential. We synthesized Fe rich FeCo core-Co rich FeCo oxyhydroxide layer with a different particle size of 173 nm, 225 nm, and 387 nm (FeCo 173, 225, 387) through a difference in the reduction rate of Fe/Co precursors using facile modified polyol synthesis. To investigate the effect of conductivity, CoFe₂O₄ nanoparticles of 80–130 nm were synthesized. Among samples, FeCo 173 showed remarkable catalytic performance of 316 mV at a current density of 10 mA/cm² in 0.1 M KOH compared to RuO₂ (408 mV), FeCo 225 (323 mV), FeCo 387 (334 mV), CoFe₂O₄ (382 mV). Moreover, FeCo 173 showed good stability for 60,000 s while RuO₂ showed a gradual increase in overpotential to maintain 10 mA/cm² after 15,000 s in chronopotentiometry. The excellent performance was attributed to Fe-rich metallic core, a small amount of Fe doping into CoOOH, and the synergic effect between the active site of Co rich FeCoOOH and conductive Fe rich metallic core. Following this result, it shows that the use of such FeCo electrodes has advantages in the production of hydrogen via electrochemical water oxidation.     

CoMo heterohierarchical foam-structured cathode for anion exchange membrane water electrolyzer

It is important to consider the synergy of heterostructures to improve the slow kinetics of water dissociation in the alkaline hydrogen evolution reaction (HER). Herein, we report a simple method to design a heterohierarchical CoMo catalyst. The CoMo catalyst was prepared by simple one-pot electrodeposition on carbon paper (CP). The CoMo/CP catalyst was optimized for the alkaline HER by controlling the electrodeposition bath conditions, potential, and time. The optimized catalyst shows the heterohierarchical structure containing the electrically conductive metallic Co in the bulk and Mo-incorporated Co containing Mo⁴⁺ at the surface. It exhibited a lower HER overpotential of 0.11 V at ?20 mA/cm² compared to those of the others owing to the synergetic effect of the between the Co and Mo incorporated Co. The results highlight the advantages of the simple method developed herein for the design of heterohierarchical catalysts.     

CuCo2O4–NiO heterostructure catalysts for hydrogen production from ammonia borane

Ammonia borane (NH₃BH₃, AB) has been considered as one of the most attractive candidates for chemical hydrogen-storage materials and chemical hydrogen generation materials. Development of low-cost and high-performance catalysts for hydrogen generation from AB is highly desirable, which is still a huge challenge. Hollow sphere CuCo₂O₄ promotes the catalytic hydrolysis of AB due to its unique hollow sphere shape and the synergistic effect of Co and Cu elements. In this study, a heterogeneous structured catalyst containing NiO and CuCo₂O₄ was developed by a simple and low-cost method in order to improve the catalytic performance of CuCo₂O₄. Initially, CuCo₂O₄ with hollow sphere structure was synthesized by hydrothermal method, and then NiO were deposited onto CuCo₂O₄ by impregnation-calcination method to form a heterogeneous structure. The CuCo₂O₄–NiO catalyst showed good catalytic activity for the hydrolysis of AB. The catalytic performance of CuCo₂O₄–NiO was then optimised by controlling the concentration of the impregnated salt solution, and the optimised catalytic performance was 1.42 times that of pure CuCo₂O₄ with a HER value of 870 mL_H2g_cat⁻¹min⁻¹. This low-cost CuCo₂O₄–NiO obtained by impregnation-calcination method is valuable for catalytic hydrogen production from AB.     

CuWO4 as a novel Z-scheme partner to construct TiO2 based stable and efficient heterojunction for photocatalytic hydrogen generation

Synthesis of highly efficient, stable, visible active CuWO₄ nanoparticles through a simple methodology, paves a feasible path for enhancing the efficiency of TiO₂. A novel nanocomposite of CuWO₄ NP loaded TiO₂ NR heterojunction was mounted through a direct Z-scheme mechanism. Optimized composite CWT-3, advances the photocatalytic hydrogen production rates of TiO₂ to 106.7 mmol h^?1 g^?1_cat. CuWO₄ incorporation as OEP compensates inefficiency of WO₃ and other Z-scheme combinations reported so far, on limiting the charge carrier recombination followed by the generation of a greater number of excitons. Specific amounts of catalyst loading, study on the effect of sacrificial reagents, and understanding the effect of the light source, are the three pivotal steps that helped here to hamper the density of overall back reactions. The formation of Z-scheme heterojunction was evidently confirmed on determining the position of CBM and VBM, PL and photoelectrochemical analysis. Recyclability studies further proved the stable and efficient outcomes of CWT-3 for five consecutive cycles. Based on photocatalytic activity, employing BDF by-product glycerol as an optimized sacrificial reagent serves the oxidation demands and triggered 53.26% solar to hydrogen conversion efficiency under natural sunlight irradiation.     

Corrosion-resistant non-noble metal electrodes for PEM-type water electrolyzer

Developing cheap and highly durable non-noble metal catalysts for water electrolysis to sustainably produce hydrogen as alternatives to platinum-based catalysts is essential. Herein, we report graphene-encapsulated NiMo alloys as acid-stable non-noble metal catalyst electrodes. The graphene-encapsulated NiMo cathode showed a highly stable performance in the potential cycling test (10,000 cycles) from 0 to 5.0 A cm⁻² and 100 h of durability at a 2.2 V constant cell voltage. A balance between catalytic activity and corrosion in acidic environments was achieved by tuning the number of N-doped graphene layers. Through their application in a full-cell PEM-type water electrolyzer, we verify that noble metal catalysts can be replaced by non-noble metal catalysts. Such cheap acid-stable non-noble metal electrodes have promising practical applications in PEM-type water electrolysis.     

Preparation and improvement of nickel catalyst supported ordered mesoporous spherical silica for thermocatalytic decomposition of methane

The thermocatalytic alteration of CH₄ into highly pure hydrogen and filaments of carbon was investigated on a series of Ni-catalysts with various contents (25, 40, 55, and 70 wt%) supported mesoporous spherical SiO₂. The silica with ordered structure and high specific surface area (1136 m²/g) was synthesized using the Stöber technique with TEOS as a silica precursor and CTAB as the template in a simple synthesis system of aqueous-phase. This technique led to the preparation of mesoporous spherical silica. The prepared samples were characterized using BET, TPR, XRD, TPO, and SEM analyses. The prepared catalysts with different nickel loading showed the BET surface area ranging from 225.0 to 725.7 m²/g. These results indicated that an increase in nickel content decreases the surface area and leads to a subsequent collapse of a pore structure. SEM analysis confirmed a spherical nanostructure of catalysts and revealed that with the increase in loading of Ni, the particle size enlarged, because of the agglomeration of the particles. The results implied that the high methane conversion of 54% obtained over the 55 wt% Ni/SiO₂ at 575 °C and this sample had higher stability at lower reaction temperature than the other prepared catalysts, slowly deactivation was observed for this catalyst at a period of 300 min of time on stream.     

Pd-decorated CNT as sensitive material for applications in hydrogen isotopes sensing - Application as gas sensor

Applicability of multiwall carbon nanotubes (MWCNTs) decorated with palladium nanoparticles as sensitive layer in a resistive microsensor for identification of hydrogen isotopes, Deuterium (²H) and Protium (¹H), has been demonstrated. Palladium nanoparticles were anchored on the MWCNTs surface via a chemical process involving micellization, from a precursor chloride solution, in high ultrasonic density field. Pd-MWCNTs are quasi-aligned between the interdigitated gold electrodes of a SiO₂ substrate by drop casting and di-electrophoretic alignment in Tetrahydrofuran (THF) and Nafion solution. The morphostructural characterization of the sensitive material has been carried out through SEM, TEM and Raman spectroscopy and its gas sensing properties were evaluated using electrical measurements performed on a series of isotope concentrations (ranging from 0.1% up to 1%, and from 1% to 4%, value to which hydrogen becomes explosive) diluted in argon, to observe the evolution of the sensor sensibility. The two hydrogen isotopes have different behaviors related to the adsorption on the Pd-MWCNT, which is well observed in the resistance change. Therefore, the sensor based on Pd-MWCNTs could be a viable solution to be integrated in systems for hydrogen leakage detection.     

Hydrogen production from additive-free formic acid over highly active metal organic frameworks-supported palladium-based catalysts

The metal organic frameworks (MOFs) supported Pd catalysts for H₂ generation from formic acid (FA) were synthesized in this work, via a facile excessive impregnation-low temperature reduction approach. Among the synthetic catalysts, 10% Pd/MOF-Cr (18) displayed a remarkable performance for catalyzing FA dehydrogenation in additive-free aqueous solution, and the corresponding TOF_mid achieved 537.8 h^?1 at 323 K. Furthermore, the bimetallic Ni–Pd alloy catalysts were prepared by the introduction of Ni in the subsequent work. Fortunately, 10% Ni_0.4Pd_0.6/MOF-Cr was found to be a highly active and fairly durable catalyst, exhibiting a TOF_mid as high as 737.9 h^?1 at 323 K with almost 100% X_FA (final) and S_H2, and remained 94% of its original activity in the third cyclic catalysis. Meanwhile, Ni was discovered to be indispensable in increasing the electron density of Pd, downsizing the immobilized metal particles and inhibiting the agglomeration of the loaded nanoparticles.     

Effect of hydrogen flow rate on the synthesis of carbon nanofiber using microwave-assisted chemical vapour deposition with ferrocene as a catalyst

Carbon nanostructure materials are becoming of considerable commercial importance, with interest growing rapidly over the decade since the discovery of carbon nanofibers. In this study, a new novel method is introduced to synthesize the carbon nanofibers by gas-phase, where a single-stage microwave-assisted chemical vapour deposition approach is used with ferrocene as a catalyst and acetylene and hydrogen as precursor gases. Hydrogen flow rate plays a significant role in the formation of carbon nanofibers, as being the carrier and reactant gas in the floating catalyst method. The effect of process parameters such as microwave power, radiation time and gas ratio of C₂H₂/H₂ was investigated statistically. The carbon nanofibers were characterized using scanning and transmission electron microscopy and thermogravimetric analysis. The analysis revealed that the optimized conditions for carbon nanofibers production were microwave power (1000 W), radiation time (35 min) and acetylene/hydrogen ratio (0.8). The field emission scanning electron microscope and transmission electron microscope analyses revealed that the vertical alignment of carbon nanofibers has tens of microns long with a uniform diameter ranging from 115 to 131 nm. High purity of 93% and a high yield of 12 g of CNFs were obtained. These outcomes indicate that identifying the optimal values for process parameters is important for synthesizing high quality and high CNF yield.     

Characteristics and performance of the Co–CeO2 catalyst as a function of the promoter (La,Pr, and Zr) used in high temperature water gas shift reaction

The catalysts used to facilitate the water gas shift reaction (WGSR) are generally harmful to the environment. Therefore, catalysts that have high activity and stability in WGSR and do not pollute the environment need to be fabricated. Herein, three promoters (La, Pr, and Zr) are added into Co–CeO₂ (CoCe) catalyst to improve catalytic performance in a high temperature WGSR to produce high-purity hydrogen from waste-derived synthesis gas. Various techniques are employed to confirm the changes in the properties that affect the catalytic performance. The catalytic reaction is performed at a high gas hourly space velocity to screen the performance of the promoted CoCe catalysts. The CoCeZr catalyst shows the highest CO conversion (X_CO = 88% at 450 °C) due to its high Co dispersion and oxygen vacancy resulting from the addition of Zr to the CoCe catalyst; thus, it is most suitable for use in high temperature WGSR.     

Turning glycerol surplus into renewable syngas through glycerol steam reforming over a sol-gel Ni–Mo2C-Al2O3 catalyst

In this work, a sol-gel Ni–Mo₂C–Al₂O₃ catalyst is employed for the first time in the glycerol steam reforming for syngas production. Catalyst stability and activity are investigated in the temperature range of 550 °C–700 °C and time on stream up to 30 h. As reaction temperature increases, from 550 °C to 700 °C, H₂ yield boosts from 22% to 60%. The stability test, carried out at milder conditions (600 °C and Gas-Hourly Space-Velocity (GHSV) of 50,000 mL h⁻¹.g_cat⁻¹), shows high catalyst stability, up to 30 h, with final conversion, H₂ yield, and H₂/CO ratio of 95%, 53% and 1.95, respectively. Both virgin and spent catalysts have been characterized by a multitude of techniques, e.g., Atomic-Absorption spectroscopy, Raman spectroscopy, N₂-adsorption-desorption, and Transmission Electron Microscopy (TEM), among others. Regarding the spent catalysts, carbon deposits’ morphology becomes more graphitic as the reaction temperature increases, and the total coke formation is mitigated by increasing reaction temperature and lowering GHSV.     

Effect of ZrO2 on the performance of Co–CeO2 catalysts for hydrogen production from waste-derived synthesis gas using high-temperature water gas shift reaction

In this study, highly active and stable CeO₂, ZrO₂, and Zr_(1-x)Ce_(x)O₂-supported Co catalysts were prepared using the co-precipitation method for the high-temperature water gas shift reaction to produce hydrogen from waste-derived synthesis gas. The physicochemical properties of the catalysts were investigated by carrying out Brunauer-Emmet-Teller, X-ray diffraction, CO-chemisorption, Raman spectroscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and H₂-temperature-programmed reduction measurements. With an increase in the ZrO₂ content, the surface area and reducibility of the catalysts increased, while the interaction between Co and the support and the dispersion of Co deteriorated. The Co–Zr_0.4Ce_0·6O₂ and Co–Zr_0.6Ce_0·4O₂ catalysts showed higher oxygen storage capacity than that of the others because of the distortion of the CeO₂ structure due to the substitution of Ce⁴⁺ by Zr⁴⁺. The Co–Zr_0.6Ce_0·4O₂ catalyst with high reducibility and oxygen storage capacity exhibited the best catalytic performance and stability among all the catalysts investigated in this study.     

Modulating Fischer-Tropsch synthesis performance on the Co3O4@SixAly catalysts by tuning metal-support interaction and acidity

ZIF-67 derived catalysts for Fischer-Tropsch synthesis have attracted much attention in recent years, while there is still a potential to improve their activity and selectivity. In this work, we prepared Si/Al co-immobilized Co₃O₄@Si_xAl_y catalysts by in-situ doping tetraethylorthosilicate and aluminum nitrate during the synthesis of ZIF-67. The effects of different Si/Al ratios on the metal-support interaction, acidity and FTS performance were explored. Results indicated that the Co₃O₄@Si₀Al₄ catalyst exhibited the best FTS performance with the CO conversion as high as 79.9% and CTY (cobalt time yield) value of 19.5 × 10^?5 mol_CO·g_Co^?1·s^?1, which was ascribed to the moderate metal-support interaction and the most active Co sites. Meanwhile, the Co₃O₄@Si₃Al₁ and Co₃O₄@Si₂Al₂ catalysts exhibited higher iso-paraffin and olefin selectivity due to more acidic sites.     

Dark fermentative biohydrogen production using pretreated Scenedesmus obliquus biomass under an integrated paradigm of biorefinery

In recent times, biohydrogen production from microalgal feedstock has garnered considerable research interests to sustainably replace the fossil fuels. The present work adapted an integrated approach of utilizing deoiled Scenedesmus obliquus biomass as feedstock for biohydrogen production and valorization of dark fermentation (DF) effluent via biomethanation. The microalgae was cultivated under different CO₂ concentration. CO₂-air sparging of 5% v/v supported maximum microalgal growth and carbohydrate production with CO₂ fixation ability of 727.7 mg L^?1 d^?1. Thereafter, lipid present in microalgae was extracted for biodiesel production and the deoiled microalgal biomass (DMB) was subjected to different pretreatment techniques to maximize the carbohydrate recovery and biohydrogen yield. Steam heating (121 °C) in coherence with H₂SO₄ (0.5 N) documented highest carbohydrate recovery of 87.5%. DF of acid-thermal pretreated DMB resulted in maximum H₂ yield of 97.6 mL g^?1 VS which was almost 10 times higher as compared to untreated DMB (9.8 mL g^?1 VS). Subsequent utilization of DF effluent in biomethanation process resulted in cumulative methane production of 1060 mL L^?1. The total substrate energy recovered from integrated biofuel production system was 30%. The present study envisages a microalgal biorefinery to produce biohydrogen via DF coupled with concomitant CO₂ sequestration.     

Producing hydrogen from the fermentation of cheese whey and glycerol as cosubstrates in an anaerobic fluidized bed reactor

This study aimed to evaluate the effect of the organic loading rate (OLR) (60, 90, and 120 g Chemical Oxygen Demand (COD). L^?1. d^?1) on hydrogen production from cheese whey and glycerol fermentation as cosubstrates (50% cheese whey and 50% glycerol on a COD basis) in a thermophilic fluidized bed reactor (55 °C). The increase in the OLR to 90 gCOD.L^?1. d^?1 favored the hydrogen production rate (HPR) (3.9 L H₂. L^?1. d^?1) and hydrogen yield (HY) (1.7 mmol H₂. gCOD^?1_app) concomitant with the production of butyric and acetic acids. Employing 16S rRNA gene sequencing, the highest hydrogen production was related to the detection of Thermoanaerobacterium (34.9%), Pseudomonas (14.5%), and Clostridium (4.7%). Conversely, at 120 gCOD.L^?1. d^?1, HPR and HY decreased to 2.5 L H₂. L^?1. d^?1 and 0.8 mmol H₂. gCOD^?1_app, respectively, due to lactic acid production that was related to the genera Thermoanaerobacterium (50.91%) and Tumebacillus (23.56%). Cofermentation favored hydrogen production at higher OLRs than cheese whey single fermentation.