Publications

The synthesis of low-cost and highly active electrodes for both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is very important for water splitting. In this work the novel amorphous iron-nickel phosphide (FeP-Ni) nanocone arrays as efficient bifunctional electrodes for overall water splitting have been in-situ assembled on conductive three-dimensional (3D) Ni foam via a facile and mild liquid deposition process. It is found that the FeP-Ni electrode demonstrates highly efficient electrocatalytic performance toward overall water splitting. In 1 M KOH electrolyte the optimal FeP-Ni electrode drives a current density of 10 mA/cm2 at an overpotential of 218 mV for the OER and 120 mV for the HER and can attain such current density for 25 h without performance regression. Moreover a two-electrode electrolyzer comprising the FeP-Ni electrodes can afford 10 mA/cm2 electrolysis current at a low cell voltage of 1.62 V and maintain long-term stability as well as superior to that of the coupled RuO2/NF‖Pt/C/NF cell. Detailed characterizations confirm that the excellent electrocatalytic performances for water splitting are attributed to the unique 3D morphology of nanocone arrays which could expose more surface active sites facilitate electrolyte diffusion benefit charge transfer and also favorable bubble detachment behavior. Our work presents a facile and cost-effective pathway to design and develop active self-supported electrodes with novel 3D morphology for water electrolysis.

In this work CdS/SiC/TiO₂ tri-composite photocatalysts that exploit electron- and hole-transfer processes were fabricated using an easy two-step method in the liquid phase. The photocatalyst with a 1:1:1 M ratio of CdS/SiC/TiO₂ exhibited a rate of hydrogen evolution from an aqueous solution of sodium sulfite and sodium sulfide under visible light of 137 μmol h⁻¹ g⁻¹ which is 9.5 times that of pure CdS. β-SiC can act as a sink for the photogenerated holes because the valence band level of β-SiC is higher than the corresponding bands in CdS and TiO2. In addition the level of the conduction band of TiO2 is lower than those of CdS and β-SiC so TiO₂ can act as the acceptor of the photogenerated electrons. Our results demonstrate that hole transfer and absorption in the visible light region lead to an effective hydrogen-production scheme.

A technoeconomic analysis of photoelectrochemical (PEC) and photovoltaic-electrolytic (PV-E) solar-hydrogen production of 10 000 kg H₂ day⁻¹ (3.65 kilotons per year) was performed to assess the economics of each technology and to provide a basis for comparison between these technologies as well as within the broader energy landscape. Two PEC systems differentiated primarily by the extent of solar concentration (unconcentrated and 10× concentrated) and two PV-E systems differentiated by the degree of grid connectivity (unconnected and grid supplemented) were analyzed. In each case a base-case system that used established designs and materials was compared to prospective systems that might be envisioned and developed in the future with the goal of achieving substantially lower overall system costs. With identical overall plant efficiencies of 9.8% the unconcentrated PEC and non-grid connected PV-E system base-case capital expenses for the rated capacity of 3.65 kilotons H₂ per year were $205 MM ($293 per m² of solar collection area (m_S⁻²) $14.7 W_H2P⁻¹) and $260 MM ($371 mS−2 $18.8 W_H2P⁻¹) respectively. The untaxed plant-gate levelized costs for the hydrogen product (LCH) were $11.4 kg⁻¹ and $12.1 kg⁻¹ for the base-case PEC and PV-E systems respectively. The 10× concentrated PEC base-case system capital cost was $160 MM ($428 m_S−2 $11.5 WH₂P⁻¹) and for an efficiency of 20% the LCH was $9.2 kg−1. Likewise the grid supplemented base-case PV-E system capital cost was $66 MM ($441 _mS⁻² $11.5 W_H2P⁻¹) and with solar-to-hydrogen and grid electrolysis system efficiencies of 9.8% and 61% respectively the LCH was $6.1 kg⁻¹. As a benchmark a proton-exchange membrane (PEM) based grid-connected electrolysis system was analyzed. Assuming a system efficiency of 61% and a grid electricity cost of $0.07 kWh⁻¹ the LCH was $5.5 kg⁻¹. A sensitivity analysis indicated that relative to the base-case increases in the system efficiency could effect the greatest cost reductions for all systems due to the areal dependencies of many of the components. The balance-of-systems (BoS) costs were the largest factor in differentiating the PEC and PV-E systems. No single or combination of technical advancements based on currently demonstrated technology can provide sufficient cost reductions to allow solar hydrogen to directly compete on a levelized cost basis with hydrogen produced from fossil energy. Specifically a cost of CO₂ greater than ∼$800 (ton CO₂)−1 was estimated to be necessary for base-case PEC hydrogen to reach price parity with hydrogen derived from steam reforming of methane priced at $12 GJ⁻¹ ($1.39 (kg H₂)⁻¹). A comparison with low CO₂ and CO₂-neutral energy sources indicated that base-case PEC hydrogen is not currently cost-competitive with electrolysis using electricity supplied by nuclear power or from fossil-fuels in conjunction with carbon capture and storage. Solar electricity production and storage using either batteries or PEC hydrogen technologies are currently an order of magnitude greater in cost than electricity prices with no clear advantage to either battery or hydrogen storage as of yet. Significant advances in PEC technology performance and system cost reductions are necessary to enable cost-effective PEC-derived solar hydrogen for use in scalable grid-storage applications as well as for use as a chemical feedstock precursor to CO₂-neutral high energy-density transportation fuels. Hence such applications are an opportunity for foundational research to contribute to the development of disruptive approaches to solar fuels generation systems that can offer higher performance at much lower cost than is provided by current embodiments of solar fuels generators. Efforts to directly reduce CO₂ photoelectrochemically or electrochemically could potentially produce products with higher value than hydrogen but many as yet unmet challenges include catalytic efficiency and selectivity and CO₂ mass transport rates and feedstock cost. Major breakthroughs are required to obtain viable economic costs for solar hydrogen production but the barriers to achieve cost-competitiveness with existing large-scale thermochemical processes for CO₂ reduction are even greater.

As of 2003 15 hydrogen refuelling stations (HRSs) have been deployed in the Netherlands. To become established the HRS has to go through a permitting procedure. An important document of the permitting dossier is the quantitative risk assessment (QRA) as it assesses the risks of the HRS associated to people and buildings in the vicinity of the HRS. In the Netherlands a generic prescribed approach exists on how to perform a QRA however specific guidelines for HRSs do not exist. An intercomparison among the QRAs of permitted HRSs has revealed significant inconsistencies on various aspects of the QRA: namely the inclusion of HRS sub-systems and components the HRS sub-system and component considerations as predefined components the application of failure scenarios the determination of failure frequencies the application of input parameters the consideration of preventive and mitigation measures as well as information provided regarding the HRS surroundings and the societal risk. It is therefore recommended to develop specific QRA guidelines for HRSs.

One of the options to reduce the dependence on fossil fuels is to produce gas with the quality of natural gas but based on renewable energy sources. It can encompass among other biogas generation from various types of biomass and its subsequent upgrading. The main aim of this study is to analyze under a combined technical economic and environmental perspective three of the most representative technologies for the production of biomethane (bio-based natural gas): (i) manure fermentation and its subsequent upgrading by CO₂ removal (ii) manure fermentation and biogas methanation using renewable hydrogen from electrolysis and (iii) biomass gasification in the atmosphere of oxygen and methanation of the resulted gas. Thermodynamic economic and environmental analyses are conducted to thoroughly compare the three cases. For these purposes detailed models in Aspen Plus software were built while environmental analysis was performed using the Life Cycle Assessment methodology. The results show that the highest efficiency (66.80%) and the lowest break-even price of biomethane (19.2 €/GJ) are reached for the technology involving fermentation and CO₂ capture. Concerning environmental assessment the system with the best environmental performance varies depending on the impact category analyzed being the system with biomass gasification and methanation a suitable trade-off solution for biomethane production.

High hydrogen content fuels can be used in gas turbine for power generation with CO₂ capture IGCC plants or with hydrogen from renewables. The challenge for the engine is the high reactive combustion properties making dilution necessary to mitigate NO_x emissions at the expense of a significant energy cost. In the concept analysed in this study high Exhaust Gas Recirculation (EGR) rate is applied to the gas turbine to generate oxygen depleted air. As a result combustion temperature is inherently limited keeping NO_x emissions low without the need for dilution or unsafe premixing. The concept is analysed by process simulation based on a reference IGCC plant with CO₂ Capture. Results with dry and wet EGR options are presented as a function EGR rate. Efficiency performance is assessed against the reference power cycle with nitrogen dilution. All EGR options are shown to represent an efficiency improvement. Nitrogen dilution is found to have a 1.3% efficiency cost. Although all EGR options investigated offer an improvement dry EGR is considered as the preferred option despite the need for higher EGR rate as compared with the wet EGR. The efficiency gain is calculated to be of 1% compared with the reference case.

In addition to methane gas higher-value resources such as hydrogen gas are produced during anaerobic wastewater treatment. They are however immediately consumed by other organisms. To recover these high-value resources not only do the desired phenotypes need to be retained in the anaerobic reactor but the undesired ones need to be washed out. In this study a well-established alginate-based polymer gel with and without a coating layer was used to selectively encapsulate hydrogen-producing biomass in beads to achieve high-rate recovery of hydrogen during anaerobic wastewater treatment. The effect of cross-linking agents Ca²+ Sr²⁺ and Ba²⁺ as well as a composite coating on the beads consisting of alternating layers of polyethylenimine and silica hydrogel were investigated with respect to their performance specifically their mass transfer characteristics and their differential ability to retain the encapsulated biomass. Although the coating reduced the escape rate of encapsulated biomass from the beads all alginate polymer matrices without coating effectively retained biomass. Fast diffusion of dissolved organic carbon (DOC) through the polymer gel was observed in both Ca-alginate and Sr-alginate without coating. The coating however decreased either the diffusivity or the permeability of the DOC depending on whether the DOC was from synthetic wastewater (more lipids and proteins) or real brewery wastewater (more sugars). Consequently the encapsulation system with coating became diffusion limited when brewery wastewater with high chemical oxygen demand was fed resulting in a lower hydrogen production rate than the uncoated encapsulation systems. In all cases the encapsulated biomass was able to produce hydrogen even at a hydraulic residence time of 45 min. Although there are limitations to this system the used of encapsulated biomass for resource recovery from wastewater shows promise particularly for high-rate systems in which the retention of specific phenotypes is desired.

Aqueous phase reforming of sorbitol was carried out in a 1.7 m long 320 mm ID microchannel reactor with a 5 mm Pt-based washcoated catalyst layer combined with nitrogen stripping. The performance of this microchannel reactor is correlated to the mass transfer properties reaction kinetics hydrogen selectivity and product distribution. Mass transfer does not affect the rate of sorbitol consumption which is limited by the kinetics of the reforming reaction. Mass transfer significantly affects the hydrogen selectivity and the product distribution. The rapid consumption of hydrogen in side reactions at the catalyst surface is prevented by a fast mass transfer of hydrogen from the catalyst site to the gas phase in the microchannel reactor. This results in a decrease of the concentration of hydrogen at the catalyst surface which was found to enhance the desired reforming reaction rate at the expense of the undesired hydrogen consuming reactions. Compared to a fixed bed reactor the selectivity to hydrogen in the microchannel reactor was increased by a factor of 2. The yield of side products (mainly C3 and heavier hydrodeoxygenated species) was suppressed while the yield of hydrogen was increased from 1.4 to 4 moles per mole of sorbitol fed.

Since the beginning of the twenty-first century the limitations of the fossil age with regard to the continuing growth of energy demand the peaking mining rate of oil the growing impact of CO₂ emissions on the environment and the dependency of the economy in the industrialized world on the availability of fossil fuels became very obvious. A major change in the energy economy from fossil energy carriers to renewable energy fluxes is necessary. The main challenge is to efficiently convert renewable energy into electricity and the storage of electricity or the production of a synthetic fuel. Hydrogen is produced from water by electricity through an electrolyser. The storage of hydrogen in its molecular or atomic form is a materials challenge. Some hydrides are known to exhibit a hydrogen density comparable to oil; however these hydrides require a sophisticated storage system. The system energy density is significantly smaller than the energy density of fossil fuels. An interesting alternative to the direct storage of hydrogen are synthetic hydrocarbons produced from hydrogen and CO₂ extracted from the atmosphere. They are CO₂ neutral and stored like fossil fuels. Conventional combustion engines and turbines can be used in order to convert the stored energy into work and heat.

Link to document download on Royal Society Website 

This session contained talks on the characterization of hydrogen-enhanced corrosion of steels and nickel-based alloys emphasizing the different observations across length scales from atomic-scale spectrographic to macro-scale fractographic examinations.

This article is the transcription of the recorded discussion of the session ‘Hydrogen Effects in Corrosion’ at the Royal Society discussion meeting Challenges of Hydrogen and Metals 16–18 January 2017. The text is approved by the contributors. M.A.S. transcribed the session and E.L.S. assisted in the preparation of the manuscript.

Link to document download on Royal Society Website