Production & Supply Chain

Functionalization of semiconductors by metallic nanoparticle is considered to be one of the most effective procedure to improve photocatalytic hydrogen production. Photodeposition is frequently used for functionalization but particle sizes and dispersions are still difficult to control. Here Pt functionalization is achieved in a one-pot synthesis. The as-prepared samples are compared to reference materials prepared by conventional photodeposition and our results confirm that small and well-dispersed nanoparticles with superior stability are obtained by one-pot synthesis. The enhanced stability is attributed to a limited leaching of Pt nanoparticles during illumination likely caused by the preferable interaction of small well dispersed Pt nanoparticles with the TiO₂ support material. In addition our results demonstrate that Na-residues are detrimental for the photocatalytic performance and washing in acidic solution is mandatory to effectively reduce the sodium contamination.

Secondary streams in biorefineries need to be valorized to improve the economic and environmental sustainability of the plants. Representative model compounds of the water fraction from the hydrothermal liquefaction (HTL) of biomass were subjected to aqueous phase reforming (APR) to produce hydrogen. Carboxylic and bicarboxylic acids hydroxyacids alcohols cycloketones and aromatics were identified as model compounds and tested for APR. The tests were performed with a Pt/C catalyst and the influence of the carbon concentration (0.3–1.8 wt. C%) was investigated. Typically the increase of the concentration negatively affected the conversion of the feed toward gaseous products without influencing the selectivity toward hydrogen production. A synthetic ternary mixture (glycolic acid acetic acid lactic acid) was subjected to APR to evaluate any differences in performance compared to the tests with single compounds. Indeed glycolic acid reacted faster in the mixture than in the corresponding single compound test while acetic acid remained almost unconverted. The influence of the reaction time temperature and carbon concentration was also evaluated. Finally residual water resulting from the HTL of a lignin-rich stream originating from an industrial-scale lignocellulosic ethanol process was tested for the first time after a thorough characterization. In this framework the stability of the catalyst was studied and found to be correlated to the presence of aromatics in the aqueous feedstock. For this reason the influence of an extraction procedure for the selective removal of these compounds was explored leading to an improvement in the APR performance.

Hydrogen will become a dominant energy carrier in the future and the efficiency and lifetime cost of its production through water electrolysis is a major research focus. Alongside efforts to offer optimum solutions through plant design and sizing it is also necessary to develop a flexible virtualised replica of renewable hydrogen plants that not only models compatibility with the “plug-and-play” nature of many facilities but that also identifies key elements for optimisation of system operation. This study presents a model for a renewable hydrogen production plant based on real-time historical and present-day datasets of PV connected to a virtualised grid-connected AC microgrid comprising different technologies of batteries electrolysers and fuel cells. Mathematical models for each technology were developed from chemical and physical metrics of the plant. The virtualised replica is the first step toward the implementation of a digital twin of the system and accurate validation of the system behaviour when updated with real-time data. As a case study a solar hydrogen pilot plant consisting of a 60 kW Solar PV a 40 kW PEM electrolyser a 15 kW LIB battery and a 5 kW PEM fuel cell were simulated and analysed. Two effective operational factors on the plant's performance are defined: (i) electrolyser power settings to determine appropriate hydrogen production over twilight periods and/or overnight and (ii) a user-defined minimum threshold for battery state of charge to prevent charge depletion overnight if the electrolyser load is higher than its capacity. The objective of this modelling is to maximise hydrogen yield while both loss of power supply probability (LPSP) and microgrid excess power are minimised. This analysis determined: (i) a hydrogen yield of 38e39% from solar DC energy to hydrogen energy produced (ii) an LPSP <2.6 104 and (iii) < 2% renewable energy lost to the grid as excess electricity for the case study.

We demonstrate a new approach for producing highly dispersed supported metal phosphide powders with small particle size improved stability and increased electrocatalytic activity towards some useful reactions. The approach involves a one-step conversion of metal supported on high surface area carbon to the metal phosphide utilising a very simple and scalable synthetic process. We use this approach to produce PdP₂ and Pd₅P₂ particles dispersed on carbon with a particle size of 4.5–5.5 nm by converting a commercially available Pd/C powder. The metal phosphide catalysts were tested for the oxygen reduction hydrogen oxidation and evolution and formic acid oxidation reactions. Compared to the unconverted Pd/C material we find that alloying the P at different levels shifts oxide formation on the Pd to higher potentials leading to greater stability during cycling studies (20% more ECSA retained 5k cycles) and in thermal treatment under air. Hydrogen absorption within the PdP₂ and Pd₅P₂ particles is enhanced. The phosphides compare favourably to the most active catalysts reported to date for formic acid oxidation especially PdP₂ and there is a significant decrease in poisoning of the surface compared to Pd alone. The mechanistic changes in the reactions studied are rationalised in terms of increased water activation on the surface phosphorus atoms of the catalyst. One of the catalysts PdP₂/C is tested in a fuel cell as anode and cathode catalyst and shows good performance.

The combination of catalytic decomposition of ammonia and in situ separation of hydrogen holds great promise for the use of ammonia as a clean energy carrier. However finding the optimal catalyst – membrane pair and operation conditions have proved challenging. Here we demonstrate that cobalt-based catalysts for ammonia decomposition can be efficiently 2 used together with a Pd-Au based membrane to produce high purity hydrogen at elevated pressure. Compared to a conventional packed bed reactor the membrane reactor offers several operational advantages that result in energetic and economic benefits. The robustness and durability of the combined system has been demonstrated for more than 1000 h on stream yielding a very pure hydrogen stream (>99.97 % H2) and recovery (>90 %). When considering the required hydrogen compression for storage/utilization and environmental issues the combined system offers the additional advantage of production of hydrogen at moderate pressures along with full ammonia conversion. Altogether our results demonstrate the possibility of deploying high pressure (350 bar) hydrogen generators from ammonia with H2 efficiencies of circa 75% without any external energy input and/or derived CO2 emissions.

Hydrogen produced by solar and other clean energy sources is an essential alternative to fossil fuels. In this study a commercial alkaline electrolyzer with different cell numbers and electrode areas are simulated for different pressure temperature thermal resistance and electrical current. This alkaline electrolyzer is considered unsteady in simulations and different parameters such as temperature are obtained in terms of time. The obtained results are compared with similar results in the literature and good agreement is observed. Various characteristics of this alkaline electrolyzer as thermoneutral voltage faraday efficiency and cell voltage are calculated and displayed. The outlet heat rate and generated heat rate are obtained as well. The pressure and the temperature in the simulations are between 1 and 100 bar and between 300 and 360 Kelvin respectively. The results show that the equilibrium temperature is reached 2-3 hours after the time when the Alkaline electrolyzer starts to work.

A redox dual-flow battery is distinct from a traditional redox flow battery (RFB) in that the former includes a secondary energy platform in which the pre-charged electrolytes can be discharged in external catalytic reactors through decoupled redox-mediated hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). The concept offers several advantages over conventional electrolysis in terms of safety durability modularity and purity. In this work we demonstrate a vanadium-manganese redox-flow battery in which Mn3+/Mn2+ and V3+/V2+ respectively mediate the OER and the HER in Mo2C-based and RuO2-based catalysts. The flow battery demonstrates an average energy efficiency of 68% at a current density of 50 mA ⋅ cm−2 (cell voltage = 1.92 V) and a relative energy density 45% higher than the conventional all-vanadium RFB. Both electrolytes are spontaneously discharged through redox-mediated HER and OER with a faradic efficiency close to 100%.

Hydrogen is often viewed as an important energy carrier in a future decarbonized world. Currently most hydrogen is produced by steam reforming of methane in natural gas (“gray hydrogen”) with high carbon dioxide emissions. Increasingly many propose using carbon capture and storage to reduce these emissions producing so-called “blue hydrogen” frequently promoted as low emissions. We undertake the first effort in a peer-reviewed paper to examine the lifecycle greenhouse gas emissions of blue hydrogen accounting for emissions of both carbon dioxide and unburned fugitive methane. Far from being low carbon greenhouse gas emissions from the production of blue hydrogen are quite high particularly due to the release of fugitive methane. For our default assumptions (3.5% emission rate of methane from natural gas and a 20-year global warming potential) total carbon dioxide equivalent emissions for blue hydrogen are only 9%-12% less than for gray hydrogen. While carbon dioxide emissions are lower fugitive methane emissions for blue hydrogen are higher than for gray hydrogen because of an increased use of natural gas to power the carbon capture. Perhaps surprisingly the greenhouse gas footprint of blue hydrogen is more than 20% greater than burning natural gas or coal for heat and some 60% greater than burning diesel oil for heat again with our default assumptions. In a sensitivity analysis in which the methane emission rate from natural gas is reduced to a low value of 1.54% greenhouse gas emissions from blue hydrogen are still greater than from simply burning natural gas and are only 18%-25% less than for gray hydrogen. Our analysis assumes that captured carbon dioxide can be stored indefinitely an optimistic and unproven assumption. Even if true though the use of blue hydrogen appears difficult to justify on climate ground

Green hydrogen is viewed as a promising energy carrier for sustainable development goals. However it has suffered from high costs hindering its implementation. For a stakeholder who considers both renewable energy and electrolysis units it is important to exploit the flexibility of such portfolios to maximize system operational revenues. To this end an electrolyser model that can characterize its dynamic behavior is required in both electric and thermal aspects. In this paper we develop a comprehensive alkaline electrolyser model that is capable of describing its hydrogen production properties temperature variations and state transitions (among production stand-by and off states). This model is further used to study the optimal dispatch of an electrolyser based on a real-world hybrid wind/electrolyser system. The results show the model can effectively capture the coupling between thermal–electric dynamics and on–off performance of an electrolyser. The flexible operation strategy based on this model is proven to significantly increase daily revenues under different spot price conditions for electricity. Comparing the model with the ones derived from conventional modeling methods reveals this model offers more operating details and highlights several operational features such as the preference for working at partial load conditions although at the expense of more computing resources. It is suggested to use this model in studies related to energy integration operation planning and control scheme development in which the multi-domain dynamic properties of electrolysers in electricity/gas/heat need to be properly characterized. A sensitivity analysis on key parameters of such electrolyser system is also introduced to connect the daily operation with long-term planning.

An independent report by the CCUS Cost Challenge Taskforce setting out the industry’s view on how best to progress carbon capture usage and storage (CCUS) in the UK in order to enable the UK to have the option of deploying CCUS at scale during the 2030s subject to costs coming down sufficiently.