Improved photon management in a photoelectrochemical cell with Nd-modified TiO2 thin film photoanode

Photon management involving particularly an up-conversion process is proposed as a relatively novel strategy for improving the efficiency of hydrogen generation in photoelectrochemical cells (PEC) with wide-band gap photoanodes. Optically active photoanode has been constructed by electrodeposition of titanium dioxide nanopowders containing Nd³⁺ ions, synthesized via a sol-gel method, onto ITO/TiO₂(thin film) substrates. Thin films of TiO₂ have been deposited by means of RF magnetron sputtering in an ultra-high-vacuum system. X-ray diffraction, scanning electron microscopy, UV-VIS-NIR spectrophotometry, and photoluminescence have been applied to assess the properties of photoanodes. In experiments involving photon-assisted water splitting, an external up-converter containing Yb³⁺/Er³⁺ rare-earth ions has been used. Photocurrent as a function of voltage (V_B) under illumination with white light is relatively high (280 μA at V_B = 0 V) for pure TiO₂ thin films and it is not affected by the electrodeposition of TiO₂:Nd³⁺ powders. NIR-driven up-conversion with laser excitation at λ = 980 nm has been found responsible for a 13-fold increase in photocurrent at V_B = 0 V in the modified PEC configuration.     

Resource potential for wind-hydrogen power in Ukraine

The paper provides an assessment of the current wind energy potential in Ukraine, and discusses developmental prospects for wind-hydrogen power generation in the country. Hydrogen utilization is a highly promising option for Ukraine's energy system, environment, and business. In Ukraine, an optimal way towards clean zero-carbon energy production is through the development of the wind-hydrogen sector. In order to make it possible, the energy potential of industrial hydrogen production and use has to be studied thoroughly.Ukraine possesses huge resources for wind energy supply. At the beginning of 2020, the total installed capacity of Ukrainian wind farms was 1.17 GW. Wind power generation in Ukraine has significant advantages in comparison to the use of traditional sources such as thermal and nuclear energy.In this work, an assessment of the wind resource potential in Ukraine is made via the geographical approach suggested by the authors, and according to the «Methodical guidelines for the assessment of average annual power generation by a wind turbine based on the long-term wind speed observation data». The paper analyses the long-term dynamics of average annual wind speed at 40 Ukrainian weather stations that provide valid data. The parameter for the vertical wind profile model is calculated based on the data reanalysis for 10 m and 50 m altitudes. The capacity factor (CF) for modern wind turbine generators is determined. The CF spatial distribution for an average 3 MW wind turbine and the power generation potential for the wind power plants across the territory of Ukraine are mapped.Based on the wind energy potential assessment, the equivalent possible production of water electrolysis-derived green hydrogen is estimated. The potential average annual production of green hydrogen across the territory of Ukraine is mapped.It is concluded that Ukraine can potentially establish wind power plants with a total capacity of 688 GW on its territory. The average annual electricity production of this system is supposed to reach up to 2174 bln kWh. Thus, it can provide an average annual production of 483 billion Nm³ (43 million tons) of green hydrogen by electrolysis. The social efficiency of investments in wind-hydrogen electricity is presented.     

Ultracompact methane steam reforming reactor based on microwaves susceptible structured catalysts for distributed hydrogen production

Hydrogen is a potential green energy vector. Since the heating of the reforming processes commonly used for its production is obtained by burning hydrocarbons, it has a substantial CO₂ footprint. One of the most critical aspects in the methane steam reforming (MSR) reaction is the heat transfer to the catalytic volume, due to the high heat fluxes required to obtain high methane conversions. Consequently, the reactor has complex geometries, along with the heating medium being characterized by temperatures higher than 1000 °C; expensive construction materials and high reaction volumes are therefore needed, resulting in slow thermal transients. These aspects increase the costs (both operative and fixed) as well as cause a decrease in the whole process efficiency. The heat transfer limitations due to the endothermicity of methane steam reforming reaction could be effectively overcome by microwave (MW) heating. This heating technique, that depends only on the dielectric properties of the materials, can result in an efficient and faster method for transferring heat directly to the catalyst, thus generating the heat directly inside the catalytic volume. In this work, Ni-based catalysts, differing from each other by the Ni loading (7 and 15 wt% with respect to the washcoat) were prepared. The catalysts were characterized by means of several techniques and tested in the MW-assisted methane steam reforming reaction. Furthermore, the energy balance of the entire process was performed to calculate the energy efficiency, making a preliminary evaluation of its feasibility in distributed hydrogen production also possible. The results of the preliminary tests showed that the prepared structured catalysts are very susceptible to the MW radiation, and that in the presence of the MSR reaction, it is possible to make the system reach a temperature of 900 °C. In the same tests, the CH₄ conversion showed a good approach to the thermodynamic equilibrium values starting at temperatures of about 800 °C at a value of gas hourly space velocity (GHSV) of about 5000 h^?1. The energy efficiency of the lab-scale system, calculated as the ratio among the energy absorbed by the system and the energy supplied by the microwaves, was about 50%. Future studies will deal with the microwave reactor optimization, aiming at the increase of the energy efficiency of the system, as well as to obtain a higher CH₄ conversion at lower temperatures and increase the H₂ yield and selectivity.     

Methylcyclohexane production under fluctuating hydrogen flow rate conditions

Energy storage using liquid organic hydrogen carrier (LOHC) is a long-term method to store renewable energy with high hydrogen energy density. This study investigated a simple and low-cost system to produce methylcyclohexane (MCH) from toluene and hydrogen using fluctuating electric power, and developed its control method. In the current system, hydrogen generated by an alkaline water electrolyzer was directly supplied to hydrogenation reactors, where hydrogen purification equipment such as PSA and TSA is not installed to decrease costs. Hydrogen buffer tanks and compressors are not equipped. In order to enable MCH production using fluctuating electricity, a feed-forward toluene supply control method was developed and introduced to the system. The electrolyzer was operated under triangular waves and power generation patterns of photovoltaic cells and produced hydrogen with fluctuating flow rates up to 7.5 Nm³/h. Consequently, relatively high purity of MCH (more than 90% of MCH mole fraction) was successfully produced. Therefore, the simplified system has enough potential to produce MCH using fluctuating renewable electricity.     

First-principles study on the dissolution and diffusion behavior of hydrogen in carbide precipitates

To understand the hydrogen (H) behavior in the carbide precipitates, the dissolution and diffusion properties of interstitial H in the transition metal carbide (TMC; TM = Hf, Nb, Ta, Ti, V, and Zr) were studied by first-principles calculations. In these carbides, it can be seen that H tends to occupy the trigonal site (tri2-site) surrounded by three transition metal atoms and one carbon atom rather than the face center (fc-site) and the body center (bc-site) which with the larger space. We found that the bonding interaction between H atom and the nearest-neighbor (1NN) carbon atom is the dominant influence on the stability of H dissolution. Besides, we obtained the temperature-dependent solubility and diffusion coefficients of H in TMC and pure vanadium through Sievert's law and transition state theory. Compared with pure vanadium, H shows the worse solubility in TMC, and it is more difficult for hydrogen to migrate in TMC, but segregate toward the interface. Furthermore, it is interesting to note that, the diffusion barrier and the H solution energy show a linear relationship for transition metal carbides in the same period. These results can help us deepen the understanding of H behavior in vanadium alloys strengthened by carbide precipitates, and furtherly providing the theoretical guidance for the design of alloys with excellent performance.     

Experimental investigation on the dynamic responses of vented hydrogen explosion in a 40-foot container

To investigate the structural dynamics of a container subjected to a vented hydrogen explosion, 48 field tests were conducted in a 40-foot container with roof vents and an end vent. The effects of the hydrogen concentration, ignition position, and obstacles on the evolution of the dynamic responses were investigated. Three stages were generally observed for displacements: (1) At the stage of the vent rupture, the displacement could be approximated as a quasi-static response, and there was a linear relationship between the peaks of positive overpressure and displacement. (2) Structural deformation appeared as reciprocating vibration at the stage of Helmholtz oscillation. (3) The structure exhibited relatively weak irregular fluctuation when high-frequency acoustic oscillation occurred. Two types of the structural acceleration with low and high amplitudes resulting from Helmholtz oscillation and acoustic oscillation, respectively, were clearly observed. For the end-vented explosion, multiple peaks were observed for the displacement at the quasi-static stage due to the rupture, discharge, and external explosion. Moreover, the displacement was sensitive to hydrogen concentration, whereas the number of obstacles and the ignition position had significant influences on the peak acceleration for roof venting. This work conducted the fundamental explanation for the evolution law of structural responses induced by vented hydrogen explosions from the perspective of structural dynamics and enriched the experimental accumulation in a large-scale container with congestion in this field.     

Concise dynamic model to accurately calculate the hydrogen yield during the reaction process

Estimation of hydrogen production rate and the total amount hydrogen during any reaction process require an accurate and concise dynamic model to describe the variation of hydrogen production rate with reaction time. There must be two comprehensive features of such model, the first one is that the hydrogen production rate calculated by this model is zero at the initial time is zero and the second one is that the integration of this model over time result in an explicit function. In this paper, we present a comprehensive model which meets above two requirements via amendments to the shifted logistic model. The model is validated against measured results through comparison of 25 experimental and theoretical hydrogen production rate. The experimentally validated model is used to calculate the total amount hydrogen during each reaction process. The impact of some experimental conditions on the total hydrogen production was mathematically explained for the first time, and this result reveal the excellent predictive ability of framework suggested in this paper. In addition, that is for an experimental condition history, predictions are achieved by developing a set of “secondary models” that describe some experimental conditions dependence of the “primary models” parameters. The method to obtain the parameters in “secondary models” described in this paper indicated that another major departure from the conventional models is the notion that the “secondary models” do not need to follow any preconceived formula and that they can be derived solely from the observed growth patterns. The presented framework can help the hydrogen production industry.     

A new catalyst based on a nickel(II) complex of diiminodiphosphine for hydrogen evolution and oxidation

Based on that hydrogen energy is widely used in fuel cells, we focus our interests on the design and research of new complexes that catalyze the reaction in both directions, such as hydrogen evolution reactions (HERs) and hydrogen oxidation reactions (HORs). A highly efficient catalyst for both hydrogen evolution and oxidation, based on a nickel(II) complex, [Ni-en-P₂](ClO₄)₂, has been designed and provided by the reaction of Ni(ClO₄)₂ with N,N′-bis[o-(diphenylphosphino)benzylidene]ethylenediamine (en-P₂) in our group. Its structure has been determined by X-ray diffraction. [Ni-en-P₂](ClO₄)₂ can electro-catalyze hydrogen evolution both from acetic acid and a neutral buffer (pH 7.0) with a turnover frequency (TOF) of 204 and 1327 mol of hydrogen per mole of catalyst per hour (H₂/mol catalyst/h) under an overpotential (OP) of 914.6 mV and 836.6 mV, respectively. [Ni-en-P₂](ClO₄)₂ also can electro-catalyze hydrogen oxidation with a TOF of 111.7 s⁻¹ under an OP of 330 mV. The results can be attributed to that [Ni^II-en-P₂](ClO₄)₂ has three good reversible redox waves at 1.01 (Ni^III/II), −0.79 (Ni^II/I) and −1.38 V (Ni^I/0) versus Fc^+/0, respectively. We hope these findings can afford a new method for the design of electrocatalysts for both H₂ evolution and H₂ oxidation.     

Synthesis and photocatalytic performance of MoS2/Polycrystalline black phosphorus heterojunction composite

As a promising catalyst for solar hydrogen production, black phosphorus (BP) has received widespread attention due to variable band gaps, high carrier mobility, and strong light absorption performance. Herein, we use MoS₂ as a cocatalyst to synthesize BP/MoS₂ catalyst with polycrystalline BP to improve photocatalytic performance under visible light irradiation. A small amount of MoS₂ can reduce the recombination of electron-hole pairs in the composite, increase carrier transport efficiency, and then improve photocatalytic performance. As expected, the 10/0.5 ratio of BP/MoS₂ catalyst exhibits the highest photocatalytic hydrogen evolution performance with a hydrogen evolution rate of 575.4 μmol h^?1 g^?1, which is 2.5 times of pure BP. Based on the results above, a simple method is provided to synthesize low-cost black phosphorus-based photocatalysts.     

Comparative techno-economic assessment of a large-scale hydrogen transport via liquid transport media

A large-scale point to point hydrogen transport is one strategy for a prospective energy import scenario for certain countries. The case for a hydrogen transport from Australia to Japan has been addressed in several studies. However, most studies lack transparency and detailed insights into the made assumptions thus a fair evaluation of different transport pathways is challenging. To address this issue, we developed a model where a large-scale point to point hydrogen transport of liquid hydrogen is compared with the transport via liquid organic hydrogen carrier (LOHC), namely via methyl cyclohexane and hydrogenated dibenzyl toluene. We analyzed, where energy is required along the different pathways, where hydrogen losses do occur and how the costs are put together. Furthermore, the influence of hydrogen feed costs is also considered. For hydrogen production costs of 5 €₂₀₁₈/kg_H2 the total delivery costs are in the range of 6.40– 8.10 €₂₀₁₈/kg_H2.