TiO2 photocatalyst with single and dual noble metal co-catalysts for efficient water splitting and organic compound removal

Photocatalysts can be used both for air cleaning and solar energy harvesting through water splitting. However, pure TiO₂ photocatalysts are often inefficient and therefore co-catalysts are needed to improve the yield. To achieve this goal, we prepared TiO₂ and deposited Pt, Ir and Ru co-catalysts on its surface. Two base TiO₂ nanoparticles were used: P25 and rutile TiO₂ synthesized via hydrothermal method. Co-catalysts were deposited by wet impregnation technique using single element and a combination of two elements (Pt and Ir or Pt and Ru), followed by annealing in either air or H₂/Ar. Annealing in reducing atmosphere increased the photocatalytic activity of oxidation of isopropanol compared to annealing in air. We demonstrated a clear influence of the co-catalysts on the photocatalytic degradation of isopropanol and on electrochemical water-splitting reaction. The platinum-containing samples showed the best HER activity.     

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.     

Thermophysical properties of the liquid organic hydrogen carrier system based on diphenylmethane with the byproducts fluorene or perhydrofluorene

Fluorene (H0-F) and perhydrofluorene (H12-F) represent process-related byproducts formed by a dehydrocyclization step in the liquid organic hydrogen carrier (LOHC) system based on diphenylmethane (H0-DPM) and dicyclohexylmethane (H12-DPM). The influence of these byproducts on the liquid viscosity, surface tension, and liquid density of the DPM-based system was experimentally determined by studying three dehydrogenated binary mixtures with H0-F mole fractions of 0.05, 0.10, and 0.20 as well as one hydrogenated binary mixture with an H12-F mole fraction of 0.10 close to 0.1 MPa from (283–573) K. The densities increase with increasing share of H0-F or H12-F by around 1% per added byproduct mole fraction of 0.1. For the surface tension, an increase relative to the values of H0-DPM or H12-DPM by up to 6% is found. The addition of H0-F to H0-DPM or H12-F to H12-DPM yields a relative increase in viscosity by up to 9% at the lowest temperature studied.     

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.     

Hydrofluoroolefin-based mixed refrigerant for enhanced performance of hydrogen liquefaction process

Hydrogen has the highest gravimetric energy density of all fuels; however, it has a low volumetric energy density, unfavorable for storage and transportation. Hydrogen is usually liquefied to meet the bulk transportation needs. The exothermic interconversion of its spin isomers is an additional activity to an already energy-intensive process. The most significant temperature drop occurs in the precooling cycle (between ?150 °C and up to ?180 °C) and consumes more than 50% of the required energy. To reduce the energy consumption and improve the exergy efficiency of the hydrogen liquefaction process, a new high-boiling component, Hydrofluoroolefin (HFO-1234yf), is added to the precooled mixed refrigerant. As a result, the specific energy consumption of precooling cycle reduces by 41.8%, from 10.15 kWh/kg_LH2 to 5.90 kWh/kg_LH2, for the overall process. The exergy efficiency of the proposed case increases by 43.7%; however, the total equipment cost is also the highest. The inflated cost is primarily due to the added ortho-to-para hydrogen conversion reactor, boosting the para-hydrogen concentration. From the perspective of bulk storage and transportation of liquid hydrogen, the simplicity of design and low energy consumption build a convincing case for considering the commercialization of the process.     

MOFs in photoelectrochemical water splitting: New horizons and challenges

Growing energy consumption with the augmentation in universal population to more than nine billion by 2050 and exhausting fossil fuel reserves necessitates a harsh revolution from non-renewable energy reservoirs to renewable energy reservoirs with zero carbon emission. In the present scenario, solar energy prompted photoelectrochemical (PEC) water splitting or “Artificial Photosynthesis” via light gripping semiconductor material, originates out as the most promising methodology in accomplishing the global energy crisis. Recent studies have amply demonstrated the potential of metal-organic frameworks (MOF) towards PEC applications. They are porous crystalline coordination polymers assembled through an appropriate choice of metal ions and multidentate organic ligands. Owing to their structural regularity and synthetic tunability, MOFs integration with PEC is considered in terms of enhancing and broadening light absorption, providing active sites and directing charge transfer dynamics. Here, we have explored MOFs role in PEC and classified them into different categories such as photosensitizers, co-catalysts, counter electrode, template and also for imparting additional stability to the electrode system. MOFs mediated PEC water splitting is promising but is still rare and in its infancy. Therefore, it is pertinent and timely to take stock of the advancements made and develop insight on the use of MOFs, as an emerging solution for the problems encountered in PEC. This review covers the basics of MOF & mainly describes various case studies done during last 10 years and providing adequate impetus to researchers for critically assessing the recent advances and challenges that are faced by scientists and researchers at large.     

Detonation propagation characteristics of H2/O2/AR in multi-angle bifurcation tubes

The propagation characteristics of the detonation wave in the bifurcated tube with the angular variation range of 30°–90° are simulated with 25% AR as dilution gas for H₂/O₂ mixture fuel at chemical equivalence ratio using the solver DCRFoam built on the OpenFOAM platform. The diffraction and reflection phenomena of detonation waves passing through bifurcation tubes with different angles are studied and analyzed. The results show that the distance from regular reflection to Mach reflection increases with the increase of the bifurcation angle so that after one reflection, the detonation forms three reflection forms with the angle of the different bifurcation tubes. After the first reflection, the detonation waves are more likely to induce the formation of transverse waves in the low-angle bifurcation tube. The lowest collision pressure after the detonation collides with the upper wall to form a secondary reflection occurs in the bifurcation tube between 50° and 60°.     

Enhancing resistance of carbon deposition and reaction stability over nickel loaded fibrous silica-alumina (Ni/FSA) for dry reforming of methane

Syngas production from the dry reforming of methane is now the most extensively utilized method for removing massive amounts of greenhouse emissions. Effective solutions towards the utilization of greenhouse gases such as CO₂ and CH₄ are scarce, except for power generation in the energy sector, which is a major source of CO₂. Herein, dry reforming of methane was experimented for the first time using an effective catalytic system composed of 5% Ni fibrous silica-alumina (FSA) that was successfully fabricated using a hydrothermal method. The characterization results from XRD, FESEM mapping, TEM, BET,XRF, FTIR, H₂-TPR, TGA/DTA, and Raman spectra demonstrated that Ni/FSA is composed of orderly Ni dispersion, small particles of Ni, robust basic sites, and high oxygen vacancies which enhanced the catalytic efficiency. The synthesized Ni/FSA also reduced coke formation and had long-term stability with no evidence of inactivation during and after the catalytic cycles. The superior activity of Ni/FSA was manifested in the high conversion rates of CH₄ and CO₂ at 97% and 92% respectively, with a H₂:CO ratio of ≈ 1. The stability of Ni/FSA was also sustained over 30 h of operation at 800 °C. The findings of the Raman, TEM, and TGA/DTA tests revealed that the spent Ni/FSA catalysts did not exhibit graphitic carbon or metal sintering in significant amounts when compared to commercial Ni–Si/Al catalysts.     

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.     

Graphite nanopowder functionalized 3-D acrylamide polymeric anode for enhanced performance of microbial fuel cell

3-D highly conductive polyvinyl formaldehyde sponges functionalized with acrylamide are fabricated using polyvinyl alcohol with varying concentrations of graphite nanopowder. The properties of the fabricated anodes are analyzed and its application in microbial fuel cells is evaluated. A comparative study with Graphite felt is also performed to evaluate its commercial viability. The presence of Hydroxyl and Amine functional groups enhanced the hydrophilic and biocompatible nature of the synthesized anodes. The phylogenetic analysis substantiated the biocompatible nature and mercury porosimetry showed macroporous nature of the fabricated anode. The highest power density of ~8 W/m² is recorded for C10 establishing solid biofilm formation. A ~94% COD removal revealed the versatility of the anode for MFC based wastewater treatment. The MFC performance was twice than that of control and was also highest among the most reported modified 3-D anodes. The durability study displayed the commercial opportunity of the anode for real-time MFC operation.     

Synthesis of binary Co–Mg–O oxide system and study of its behavior in reduction/oxidation cycling

The nanoscale Co–Mg–O oxide sample (15 wt% in terms of Co₃O₄) was prepared from the corresponding xerogel synthesized by the modified sol-gel method. The hydrolysis of as-prepared Mg(OCH₃)₂ was carried out using the aqueous solution of Co(NO₃)₂ precursor. The CoO_x nanocrystallites of about 10–20 nm in size were shown to be uniformly distributed within the MgO matrix. The reduction of Co–Mg–O in H₂ flow was found to proceed in two separate stages within the temperature ranges of 200–350 °C and 350–600 °C. The prepared binary Co–Mg–O system was demonstrated to possess completely reproducible reduction behavior in the consecutive reduction/reoxidation cycles. The phase composition of the sample exposed to both the reducing and oxidative environment was followed by an in situ X-ray diffraction analysis performed at temperatures of 25, 300, 500 and 700 °C. The determined lattice parameters for MgO (a = 4.219 Å) and Co₃O₄ (a = 8.110 Å) were found to be slightly increased as compared with the values from Powder Diffraction File, so that the formation of joint non-stoichiometric (Mg_1-xCo_x)O and (Co_3-xMg_x)O₄ phases was suggested. The strong chemical interaction of cobalt oxide with MgO matrix was also evidenced by the data of a diffuse reflectance UV–vis spectroscopy.     

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.     

A review on pretreatment methods,photobioreactor design and metabolic engineering approaches of algal biomass for enhanced biohydrogen production

The development of alternative fuels has been promoted by the extreme fossil fuel consumption brought on by urbanisation and deteriorating pollution. Due to its high energy and combustible qualities, biohydrogen has been perceived as a potential fuel substitute in dealing with issues related to the rising emission of greenhouse gases and global warming. As a source of carbon sequestration and sustainable renewable energy, biohydrogen synthesis by algae species has been prevalent in research scale. This review focuses on the novel and recent metabolic approaches for enhanced algal based biohydrogen production. Pretreatment methods available and scaling techniques used for enhancing the biohydrogen productivity using algal species have been elaborated in the review. Algal characteristics that make them suitable alternative for biohydrogen production are discussed briefly. Various pretreatment methods such as physical, chemical, biological and thermal are elaborated. In addition, the factors involved in influencing the biohydrogen productivity and the metabolic engineering approaches for modifying the pathway in algae are highlighted. Scaling up of process using different types of photobioreactors such as tubular, flat panel, airlift and stirred tank are reported that briefs about merits and demerits of each photobioreactor.     

Polyaniline sensitized Pt@TiO2 for visible-light-driven H2 generation

Polyaniline is a typical conducting polymer with high migration electron rate, good stability, eco-friendly properties, and high absorption coefficients for visible light. In the present study, polyaniline decorated Pt@TiO₂ for visible light-driven H₂ generation is reported for the first time. The above-mentioned nanocomposite is prepared through a simple oxidative-polymerization and characterized by infrared spectroscopy, transmission electron microscopy, X–ray diffraction, thermogravimetric analysis, and ultraviolet–visible diffuse reflectance spectra. Polyaniline modification improves the absorption of the nanocomposite in visible light region via a photosensitization effect similar to dye–sensitization but does not influence the crystal structure and size of Pt@TiO₂. The polyaniline modified Pt@TiO₂ exhibits a remarkable visible light activity (61.8 μmol h⁻¹ g⁻¹) and good stability for H₂ generation (with an average apparent quantum yield of 10.1%) with thioglycolic acid as an electron donor. This work provides new insights into using conducting polymers, including polyaniline, as a sensitizer to modify Pt@TiO₂ for visible-light hydrogen generation.     

Biomass gasification coupled with producer gas cleaning,bottling and HTS catalyst treatment for H2-rich gas production

The aim of the present study is to demonstrate the production of hydrogen-rich fuel gas from J. curcas residue cake. A comprehensive experimental study for the production of hydrogen rich fuel gas from J. curcas residue cake via downdraft gasification followed by high temperature water gas shift catalytic treatment has been carried out. The gasification experiments are performed at different equivalence ratios and performance of the process is reported in terms of producer gas composition & its calorific value, gas production rate and cold gas efficiency. The producer gas is cleaned of tar and particulate matters by passing it through venturi scrubber followed by sand bed filter. The clean producer gas is then compressed at 0.6 MPa and bottled into a gas cylinder. The bottled producer gas and a simulated mixture of producer gas are then subjected to high temperature shift (HTS) catalytic treatment for hydrogen enriched gas production. The effect of three different operating parameters GHSV, steam to CO ratio and reactor temperature on the product gas composition and CO conversion is reported. From the experimental study it is found that, the presence of oxygen in the bottled producer gas has affected the catalyst activity. Moreover, higher concentration of oxygen concentration in the bottled producer gas leads to the instantaneous deactivation of the HTS catalyst.     

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.     

Effect of physical activation/surface functional groups on wettability and electrochemical performance of carbon/activated carbon aerogels based electrode materials for electrochemical capacitors

Polymeric carbon/activated carbon aerogels were synthesized through sol-gel polycondensation reaction followed by the carbonization at 800 °C under Argon (Ar) atmosphere and subsequent physical activation under CO₂ environment at different temperatures with different degrees of burn-off. Significant increase in BET specific surface area (SSA) from 537 to 1775 m²g⁻¹ and pore volume from 0.24 to 0.94 cm³g⁻¹ was observed after physical activation while the pore size remained constant (around 2 nm). Morphological characterization of the carbon and activated carbons was conducted using X-ray diffraction (XRD) and Raman spectroscopy. Fourier-transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) were used to investigate the effect of thermal treatment (surface cleaning) on the chemical composition of carbon samples.Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were used to analyse the capacitive and resistive behaviour of non-activated/activated/and surface cleaned activated carbons employed as electroactive material in a two electrode symmetrical electrochemical capacitor (EC) cell with 6 M KOH solution used as the electrolyte.CV measurements showed improved specific capacitance (SC) of 197 Fg⁻¹ for activated carbon as compared to the SC of 136 Fg⁻¹ when non-activated carbon was used as electroactive material at a scan rate of 5 mVs⁻¹. Reduction in SC from 197 Fg⁻¹ to 163 Fg⁻¹ was witnessed after surface cleaning at elevated temperatures due to the reduction of surface oxygen function groups.The result of EIS measurements showed low internal resistance for all carbon samples indicating that the polymeric carbons possess a highly conductive three dimensional crosslinked structure. Because of their preferred properties such as controlled porosity, exceptionally high specific surface area, high conductivity and desirable capacitive behaviour, these materials have shown potential to be adopted as electrode materials in electrochemical capacitors.     

Novel sonochemical synthesis of Zn2V2O7 nanostructures for electrochemical hydrogen storage

Although utilization of diverse classes of metal oxides as hydrogen storage materials has been reported, but there is still a major need to introduce efficient materials. Herein, mesoporous Zn₂V₂O₇ nanostructures were produced by a new sonochemical method using hydrazine, zinc nitrate, and ammonium vanadate as the starting reagents and then annealed at 700 °C. Prior to annealing, Zn₃V₃O₈ was produced in the presence of ultrasonic waves, whereas in the absence of ultrasonic waves, Zn₂(VO₄)₂ was the major product. In fact, ultrasonic waves interfered with the reaction mechanism and reduced V⁵⁺ to V⁴⁺ and V³⁺. Because of the proper composition and structure of these nanostructures, they were used for electrochemical storage of hydrogen. Storage of over 2899 mAh/g after 20 cycles by flower-like nanostructures revealed their high capability. The results also showed that morphology affects efficiency such that three-dimensional spherical nanostructures had a storage capacity of 2247 mAh/g after 20 cycles.     

Improving inter-plant integration of syngas production technologies by the recycling of CO2 and by-product of the Fischer-Tropsch process

This paper deals with the emission reduction in synthesis-gas production by better integration and increasing the energy efficiency of a high-temperature co-electrolysis unit combined with the Fischer-Tropsch process. The investigated process utilises the by-product of Fischer-Tropsch, as an energy source and carbon dioxide as a feedstock for synthesis gas production. The proposed approach is based on adjusting process streams temperatures with the further synthesis of a new heat exchangers network and optimisation of the utility system. The potential of secondary energy resources was determined using plus/minus principles and simulation of a high-temperature co-electrolysis unit. The proposed technique maximises the economic and environmental benefits of inter-unit integration. Two scenarios were considered for sharing the high-temperature co-electrolysis and the Fischer-Tropsch process. In the first scenario, by-products from the Fischer-Tropsch process were used as fuel for a high-temperature co-electrolysis. Optimisation of secondary energy sources and the synthesis of a new heat exchanger network reduce fuel consumption by 47% and electricity by 11%. An additional environmental benefit is reflected in emission reduction by 25,145 tCO₂/y. The second scenario uses fossil fuel as a primary energy source. The new exchanger network for the high-temperature co-electrolysis was built for different energy sources. The use of natural gas resulted in total annual costs of the heat exchanger network to 1,388,034 USD/y, which is 1%, 14%, 116% less than for coal, fuel oil and LPG, respectively. The use of natural gas as a fuel has the lowest carbon footprint of 7288 tCO₂/y. On the other hand, coal as an energy source has commensurable economic indicators that produce 2 times more CO₂, which can be used as a feedstock for a high-temperature co-electrolysis. This work shows how in-depth preliminary analysis can optimise the use of primary and secondary energy resources during inter-plant integration.     

Reinforcement learning based energy management systems and hydrogen refuelling stations for fuel cell electric vehicles: An overview

This paper examines the current state of the art of hydrogen refuelling stations-based production and storage systems for fuel cell hybrid electric vehicles (FCHEV). Nowadays, the emissions are increasing rapidly due to the usage of fossil fuels and the demand for hydrogen refuelling stations (HRS) is emerging to replace the conventional vehicles with FCHEVs. Hence, the availability of HRS and its economic aspects are discussed. In addition, a comprehensive study is presented on the energy storage systems such as batteries, supercapacitors and fuel cells which play a major role in the FCHEVs. An energy management system (EMS) is essential to meet the load requirement with effective utilisation of power sources with various optimizing techniques. A detailed comparative analysis is presented on the merits of Reinforcement learning (RL) for the FCHEVs. The significant challenges are discussed in depth with potential solutions for future work.