Synthesis and characterization of transition metal mixed oxide doped graphene embedded durable electrocatalyst for hydrogen evolution reaction

A promising electrocatalyst containing variable percentage of V₂O₅–TiO₂ mixed oxide in graphene oxide support was prepared by embedding the catalyst on Cu substrate through facile electroless Ni–Co–P plating for hydrogen evolution reaction. The solvothermal decomposition method was opted for tuning the crystalline characteristics of prepared material. The optimized mixed oxide was well characterized, active sites centres were identified and explained by X-ray diffraction, high resolution tunnelling electron microscopy, scanning electron microscopy coupled with energy dispersive X-ray and X-ray photon spectroscopy analysis. The structural and electronic characteristics of material was done by fourier transform infrared spectroscopy and the electrochemical behaviour of the prepared material was evaluated by using Tafel plot, electrochemical impedance analysis, linear sweep voltammetry, open circuit analysis and chronoamperometry measurements. The results show the enhanced catalytic activity of Ni–Co–P than pure Ni–P plate, due to synergic effect. Moreover, the prepared mixed oxide incorporated Ni–Co–P plate has a high activity towards HER with low over potential of 101 mV, low Tafel slope of 36 mVdec^?1, high exchange current density of 9.90 × 10^?2 Acm^?2.     

Current trends in structural development and modification strategies for metal-organic frameworks (MOFs) towards photocatalytic H2 production: A review

Photocatalytic H₂ generation using semiconductor photocatalysts is considered as a cost-effective and eco-friendly technology for solar to energy conversion; however, the present photocatalysts have been recognized to depict low efficiency. Currently, porous coordination polymers known as metal-organic frameworks (MOFs) constituting flexible and modifiable porous structure and having excess active sites are considered to be appropriate for photocatalytic H₂ production. This review highlights current progress in structural development of MOF materials along with modification strategies for enhanced photoactivity. Initially, the review discusses the photocatalytic H₂ production mechanism with the concepts of thermodynamics and mass transfer with particular focus on MOFs. Elaboration of the structural categories of MOFs into Type I, Type II, Type III and classification of MOFs for H₂ generation into transition metal based, post-transition metal based, noble-metal based and hetero-metal based has been systematically discussed. The review also critically deliberate various modification approaches of band engineering, improvement of charge separation, efficient irradiation utilization and overall efficiency of MOFs including metal modification, heterojunction formation, Z-scheme formation, by introducing electron mediator, and dye based composites. Also, the MOF synthesized derivatives for photocatalytic H₂ generation are elaborated. Finally, future perspectives of MOFs for H₂ generation and approaches for efficiency improvement have been suggested.     

Development of a H2-permeable Pd60Cu40-based composite membrane using a reverse build-up method

A new reverse build-up method is developed to fabricate an economical H₂-permeable composite membrane. Sputtering and electroplating are used for the formation of a membrane comprised of a 3.7-μm-thick Pd₆₀Cu₄₀ (wt.%) alloy layer and a 13-μm-thick porous Ni support layer, respectively. The H₂-permeation measurements are performed under the flow of a gaseous mixture of H₂ and He at 300–320 °C and 50–100 kPa of H₂ partial pressure. The H₂/He selectivity values exceed 300. The activation energy at 300–320 °C is 10.9 kJ mol⁻¹. The H₂ permeability of the membrane is 1.25 × 10⁻⁸ mol m⁻¹ s⁻¹ Pa^−0.5 at 320 °C after 448 h. The estimated Pd cost of the proposed membrane is approximately 1/8 of the cost for a pure Pd₆₀Cu₄₀ membrane. This study demonstrates that the proposed method allows the facile production of low-cost, Pd-based membranes for H₂ separation.     

Dysprosium doped copper oxide (Cu1-xDyxO) nanoparticles enabled bifunctional electrode for overall water splitting

The production of hydrogen, a favourable alternative to an unsustainable fossil fuel remains as a significant hurdle with the pertaining challenge in the design of proficient, highly productive and sustainable electrocatalyst for both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Herein, the dysprosium (Dy) doped copper oxide (Cu_1-xDy_xO) nanoparticles were synthesized via solution combustion technique and utilized as a non-noble metal based bi-functional electrocatalyst for overall water splitting. Due to the improved surface to volume ratio and conductivity, the optimized Cu_1-xDy_xO (x = 0.01, 0.02) electrocatalysts exhibited impressive HER and OER performance respectively in 1 M KOH delivering a current density of 10 mAcm^?2 at a potential of ?0.18 V vs RHE for HER and 1.53 V vs RHE for OER. Moreover, the Dy doped CuO electrocatalyst used as a bi-functional catalyst for overall water splitting achieved a potential of 1.56 V at a current density 10 mAcm^?2 and relatively high current density of 66 mAcm^?2 at a peak potential of 2 V. A long term stability of 24 h was achieved for a cell voltage of 2.2 V at a constant current density of 30 mAcm^?2 with only 10% of the initial current loss. This showcases the accumulative opportunity of dysprosium as a dopant in CuO nanoparticles for fabricating a highly effective and low-cost bi-functional electrocatalyst for overall water splitting.     

Techno-economical evaluations of decarbonized hydrogen production based on direct biogas conversion using thermo-chemical looping cycles

Hydrogen production by biogas conversion represent a promising solution for reduction of fossil CO₂ emissions. In this work, a detailed techno-economic analysis was performed for decarbonized hydrogen production based on biogas conversion using calcium and chemical looping cycles. All evaluated concepts generate 100,000 Nm³/h high purity hydrogen. As reference cases, the biogas steam reforming design without decarbonization and with CO₂ capture by gas-liquid chemical absorption were also considered. The results show that iron-based chemical looping design has higher energy efficiency compared with the gas-liquid absorption case by 2.3 net percentage points as well as a superior carbon capture rate (99% vs. 65%). The calcium looping case shows a lower efficiency than chemical scrubbing, with about 2.5 net percentage points, but the carbon capture rate is higher (95% vs. 65%). The hydrogen production cost increases with decarbonization, the calcium looping shows the most favourable situation (37.14 €/MWh) compared to the non-capture steam reforming case (33 €/MWh) and MDEA and iron looping cases (about 42 €/MWh). The calcium looping case has the lowest CO₂ avoidance cost (10 €/t) followed by iron looping (20 €/t) and MDEA (31 €/t) cases.     

Optimization of flow in additively manufactured porous columns with graded permeability

Chemical engineering systems often involve a functional porous medium, such as in catalyzed reactive flows, fluid purifiers, and chromatographic separations. Ideally, the flow rates throughout the porous medium are uniform, and all portions of the medium contribute efficiently to its function. The permeability is a property of a porous medium that depends on pore geometry and relates flow rate to pressure drop. Additive manufacturing techniques raise the possibilities that permeability can be arbitrarily specified in three dimensions, and that a broader range of permeabilities can be achieved than by traditional manufacturing methods. Using numerical optimization methods, we show that designs with spatially varying permeability can achieve greater flow uniformity than designs with uniform permeability. We consider geometries involving hemispherical regions that distribute flow, as in many glass chromatography columns. By several measures, significant improvements in flow uniformity can be obtained by modifying permeability only near the inlet and outlet.     

Bifunctional nanoporous ruthenium-nickel alloy nanowire electrocatalysts towards oxygen/hydrogen evolution reaction

A class of ruthenium-nickel alloy catalysts featured with nanoporous nanowires (NPNWs) were synthesized by a strategy combining rapid solidification with two-step dealloying. RuNi NPNWs exhibit excellent electrocatalytic activity and stability for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in which the RuNi-2500 NPNWs catalyst shows an OER overpotential of 327 mV to deliver a current density of 10 mA cm^?2 and the RuNi-0 NPNWs catalyst requires the overpotential of 69 mV at 10 mA cm^?2 showing the best HER activity in alkaline media. Moreover, the RuNi-1500 NPNWs catalyst was used as the bifunctional electrocatalyst in a two-electrode alkaline electrolyzer for water splitting, which exhibits a low cell voltage of 1.553 V and a long-term stability of 24 h at 10 mA cm^?2, demonstrating that the RuNi NPNWs catalysts can be considered as promising bifunctional alkaline electrocatalysts.     

NiFe layered double hydroxide as an efficient bifunctional catalyst for electrosynthesis of hydrogen peroxide and oxygen

Two electron oxygen reduction reaction to produce hydrogen peroxide (H₂O₂) is a promising alternative technique to the multistep and high energy consumption anthraquinone process. Herein, Ni–Fe layered double hydroxide (NiFe-LDH) has been firstly demonstrated as an efficient bifunctional catalyst to prepare H₂O₂ by electrochemical oxygen reduction (2e^? ORR) and oxygen evolution reaction (OER). Significantly, the NiFe-LDH catalyst possesses a high faraday efficiency of 88.75% for H₂O₂ preparation in alkaline media. Moreover, the NiFe-LDH catalyst exhibits excellent OER electrocatalytic property with small overpotential of 210 mV at 10 mA cm^?2 and high stability in 1 M KOH solution. On this basis, a new reactor has been designed to electrolyze oxygen and generate hydrogen peroxide. Under the ultra-low cell voltage of 1 V, the H₂O₂ yield reaches to 47.62 mmol g_cat^?1 h^?1. In order to evaluate the application potential of the bifunctional NiFe-LDH catalyst for H₂O₂ preparation, a 1.5 V dry battery has been used as the power supply, and the output of H₂O₂ reaches to 83.90 mmol g_cat^?1 h^?1. The excellent electrocatalytic properties of 2e^? ORR and OER make NiFe-LDH a promising bifunctional electrocatalyst for future commercialization. Moreover, the well-designed 2e^? ORR-OER reactor provides a new strategy for portable production of H₂O₂.     

Operation principles for hydrogen spark ignited direct injection engines for passenger car applications

The sustainable reduction of greenhouse gas emissions from road transport requires solutions to achieve net-zero carbon dioxide emissions. Therefore, in addition to vehicles with electrified powertrains, such as those implemented in battery electric of fuel cell vehicles, internal combustion engines fueled with e-fuels or biofuels are also under discussion. An e-fuel that has come into focus recently, is hydrogen due to its potential to achieve zero tank-to-wheel and well-to-wheel carbon dioxide emissions when the electrolysis is powered by electricity from renewable sources. Due to the high laminar burning velocity, hydrogen has the potential for engine operation with high cylinder charge dilution by e.g. external exhaust gas recirculation or enleanment, resulting in increased efficiency. On the other hand, the high burning velocity and high adiabatic flame temperatures pose a challenge for engine cooling due to increased heat losses compared to conventional fuels. To further evaluate the use of hydrogen for small passenger car engines, a series production 1 L 3 cylinder gasoline engine provided by Ford Werke GmbH was modified for hydrogen direct injection. The engine was equipped with a high pressure external exhaust gas recirculation system to investigate charge dilution at stoichiometric operation. Due to limitations of the turbocharging system, very lean operation, which can achieve nitrogen oxides raw emissions below 10 ppm, was limited to part load operation below BMEP = 8 bar. Thus, a reduction of the nitrogen oxides emission level at high loads compared to stoichiometric operation was not possible. At stoichiometric operation with external exhaust gas recirculation engine efficiency can be increased significantly. The comparison of stoichiometric hydrogen and gasoline operation shows a reduced indicated efficiency with hydrogen with significant faster combustion of hydrogen at comparable centers of combustion. However, higher boost pressures would allow to achieve even higher indicated efficiencies by charge dilution compared to gasoline engine operation.     

Estimates of daily oxygen consumption,carbon dioxide and methane emissions,and heat production for beef and dairy cattle using spot gas sampling

A simulation study was conducted to examine accuracy of estimating daily O₂ consumption, CO₂ and CH₄ emissions, and heat production (HP) using a spot sampling technique and to determine optimal spot sampling frequency (FQ). Data were obtained from 3 experiments where daily O₂ consumption, emissions of CO₂ and CH₄, and HP were measured using indirect calorimetry (respiration chamber or headbox system). Experiment 1 used 8 beef heifers (ad libitum feeding; gaseous exchanges measured every 30 min over 3 d in respiration chambers); Experiment 2 used 56 lactating Holstein-Friesian cows (restricted feeding; gaseous exchanges measured every 12 min over 3 d in respiration chambers); Experiment 3 used 12 lactating Jersey cows (ad libitum feeding; gaseous exchanges measured every hour for 1 d using headbox style chambers). Within experiment, averages of all measurements (FQALL) and averages of measurements selected at time points with 12, 8, 6, or 4 spot sampling FQ (i.e., sampling every 2, 3, 4, and 6 h in a 24-h cycle, respectively; FQ12, FQ8, FQ6, and FQ4, respectively) were compared. Within study a mixed model was used to compare gaseous exchanges and HP among FQALL, FQ12, FQ8, FQ6, and FQ4, and an interaction of dietary treatment by FQ was examined. A regression model was used to evaluate accuracy of spot sampling within study [i.e., FQALL (observed) vs. FQ12, FQ8, FQ6, or FQ4 (estimated)]. No interaction of diet by FQ was observed for any variables except for CH₄ production in experiment 1. No FQ effect was observed for gaseous exchanges and HP except in experiment 2 where CO₂ production was less (5,411 vs. 5,563 L/d) for FQ4 compared with FQALL, FQ12, and FQ8. A regression analysis between FQALL and each FQ within study showed that slopes and intercepts became farther from 1 and 0, respectively, for almost all variables as FQ decreased. Most variables for FQ12 and FQ8 had root mean square prediction error (RMSPE) less than 10% of the mean and concordance correlation coefficient (CCC) greater than 0.80, and RMSPE increased and CCC decreased as FQ decreased. When a regression analysis was conducted with combined data from the 3 experiments (mixed model with study as a random effect), results agreed with those from the analysis for the individual studies. Prediction errors increased and CCC decreased as FQ decreased. Generally, all the estimates from FQ12, FQ8, FQ6, and FQ4 had RMSPE less than 10% of the means and CCC greater than 0.90 except for FQ6 and FQ4 for O₂ consumption and CH₄ production. In conclusion, the spot sampling simulation with 3 indirect calorimetry experiments indicated that FQ of at least 8 samples (every 3 h in a 24-h cycle) was required to estimate daily O₂ consumption, CO₂ and CH₄ production, and HP and to detect changes in those in response to dietary treatments. This sampling FQ may be considered when using techniques that measure spot gas exchanges such as the GreenFeed and face mask systems.