Production Of Chemical Fuels Research Articles

Engineering MOF/carbon nitride heterojunctions for effective dual photocatalytic CO2 conversion and oxygen evolution reactions.

Photocatalysis appears as one of the most promising avenues to shift towards sustainable sources of energy, owing to its ability to transform solar light into chemical energy, e.g. production of chemical fuels via oxygen evolution (OER) and CO2 reduction (CO2RR) reactions. Ti metal-organic frameworks (MOFs) and graphitic carbon nitride derivatives, i.e. poly-heptazine imides (PHI) are appealing CO2RR and OER photo-catalysts respectively. Engineering of an innovative Z-scheme heterojunction by assembling a Ti-MOF and PHI offers an unparalleled opportunity to mimick an artificial photosynthesis device for dual CO2RR/OER catalysis. Along this path, understanding of the photophysical processes controlling the MOF/PHI interfacial charge recombination is vital to fine tune the electronic and chemical features of the two components and devise the optimum heterojunction. To address this challenge, we developed a modelling approach integrating force field Molecular Dynamics (MD), Time-Dependent Density Functional Theory (TD-DFT) and Non-Equilibrium Green Function DFT (NEGF-DFT) tools with the aim of systematically exploring the structuring, the opto-electronic and transport properties of MOF/PHI heterojunctions. We revealed that the nature of the MOF/PHI interactions, the interfacial charge transfer directionality and the absorption energy windows of the resulting heterojunctions can be fine tuned by incorporating Cu species in the MOF and/or doping PHI with mono- or divalent cations. Interestingly, we demonstrated that the interfacial charge transfer can be further boosted by engineering MOF/PHI device junctions and application of negative bias. Overall, our generalizable computational methodology unravelled that the performance of CO2RR/OER photoreactors can be optimized by chemical and electronic tuning of the components but also by device design based on reliable structure-property rules, paving the way towards practical exploitation.

2D numerical modeling for plasma-assisted CO2 pooling in supersonic nozzles: importance of a proper nozzle contour design

Plasma assisted CO2 dissociation has recently been the topic of many studies. The production of chemical fuels from environmentally unfriendly CO2 through supersonic nozzles is one of the most prominent approaches under investigation. However, the experiments show that the theoretical conversion rates are far away from being achieved. In this study, two-dimensional fully coupled cases are investigated. This brings insights about how the CO2 dissociation can be improved; mainly by a correct design of nozzles. The proper shape of a nozzle is a fundamental aspect to be taken into account numerically and in experiments to avoid undesirable phenomena such as the occurrence of shocks. The proper design of the nozzle shape leads to a shock-free flow being uniform at the nozzle outlet. A high degree of cooling can be achieved in a shock-free nozzle. Moreover it is shown that there is no optimal value for Mach number provided that the nozzles are sized properly. If the sizing is done correctly, it is found that higher Mach numbers lead to higher degree of non-equilibrium and thereby to higher dissociation rate. The sizing of the nozzle to maximize the departure from equilibrium in the nozzle is the final key of an efficient CO2 dissociation. Finally, the results are compared with those of a semi-analytical method to conclude that if the nozzle is conceived in a proper way, simpler approaches can also give satisfactory results.

Few-layer WS2–MoS2 in-plane heterostructures for efficient photocatalytic hydrogen evolution

Abstract Although efficient H2 evolution through water splitting under irradiation with light would solve severe global environmental and energy issues, finding efficient and eco-friendly photocatalysts from earth-abundant elements remains challenging. In this paper, we report WS2–MoS2 in-plane few-layer heterostructures that function as efficient photocatalysts. Because of the built-in potential at the epitaxially–grown WS2–MoS2 interface, the electron-hole carriers underwent rapid separation upon irradiation with light, such that the H2 generation yield rate reached as high as 9.83 mmol g–1 h–1. This improved photocatalytic H2 evolution from purely two-dimensional in-plane heterostructures has the potential to deliver outstanding catalysts for solar energy conversion as well as the production of chemical fuels.

Interplay of material thermodynamics and surface reaction rate on the kinetics of thermochemical hydrogen production

Production of chemical fuels using solar energy has been a field of intense research recently, and two-step thermochemical cycling of reactive oxides has emerged as a promising route. In this process, the oxide of interest is cyclically exposed to an inert gas, which induces (partial) reduction of the oxide at a high temperature, and to an oxidizing gas of either H2O or CO2 at the same or lower temperature, which reoxidizes the oxide, releasing H2 or CO. Thermochemical cycling of porous ceria was performed here under realistic conditions to identify the limiting factor for hydrogen production rates. The material, with 88% porosity and moderate specific surface area, was reduced at 1500 °C under inert gas with 10 ppm residual O2, then reoxidized with H2O under flow of 600 sccm g−1 of 20% H2O in Ar to produce H2. The fuel production process transitions from one controlled by surface reaction kinetics at temperatures below ∼1000 °C to one controlled by the rate at which the reactant gas is supplied at temperatures above ∼1100 °C. The reduction of ceria, when heated from 800 to 1500 °C, is observed to be gas limited at a temperature ramp rate of 50 °C min−1 at a flow of 1000 sccm g−1 of 10 ppm O2 in Ar. Consistent with these observations, application of Rh catalyst particles improves the oxidation rate at low temperatures, but provides no benefit at high temperatures for either oxidation or reduction. The implications of these results for solar thermochemical reactors are discussed.

Maximizing fuel production rates in isothermal solar thermochemical fuel production

Production of chemical fuels by isothermal pressure-swing cycles has recently generated significant interest. In this process a reactive oxide is cyclically exposed to an inert gas, which induces partial reduction of the oxide, and to an oxidizing gas of either H2O or CO2, which reoxidizes the oxide, releasing H2 or CO. At sufficiently high temperatures and sufficiently low gas flow rates, both the reduction and oxidation steps become limited only by the flow of gas across the material and not by material kinetic factors. In this contribution, we develop a numerical model describing fuel production rates in this gas-phase limited regime. The implications of this behavior are explored under all possible isothermal pressure-swing cycling conditions, and the outcome is optimized in terms of fuel production rate as well as fuel conversion and utilization of input gas of all types. Fuel production rate is maximized at infinitesimally small cycle times and attains a value that is independent of material thermodynamics. Gas utilization is maximized at infinitesimally small gas inputs, but the values can be made independent of cycle time, depending on manipulation of flow conditions. Gas-phase conditions (temperature, oxidant and reductant gas partial pressures, and CO2 vs H2O as oxidant) have a strong impact on fuel production metrics. Under realistic, finite cycle times, material thermodynamics play a measurable role in establishing fuel production rates.

A review of solar methane reforming systems

Because of the increasing demand for energy and the associated rise in greenhouse gas emissions, there is much interest in the use of renewable sources such as solar energy in electricity and fuels generation. One problem with solar energy, however, is that it is difficult to economically convert the radiation into usable energy at the desired locations and times, both daily and seasonally. One method to overcome this space-time intermittency is through the production of chemical fuels. In particular, solar reforming is a promising method for producing chemical fuels by reforming and/or water/carbon dioxide splitting. In this paper, a review of solar reforming systems is presented, as well as a comparison between these systems and a discussion on areas for potential innovation including chemical looping and membrane reactors. Moreover, a brief overview of catalysis in the context of reforming is presented.

Electrochemical-driven water splitting catalyzed by a water-soluble cobalt(II) complex supported by N,N′-bis(2′-pyridinecarboxamide)-1,2-benzene with high turnover frequency

The oxidation and reduction of water is a key challenge in the production of chemical fuels from electricity. Reported here is a soluble cobalt (II) complex, [Co(bpbH2)Cl2] 1 (bpbH2: N,N′-bis(2′-pyridinecarboxamide)-1,2-benzene), a highly active homogeneous electrocatalyst for both electrolytic water oxidation and reduction in purely aqueous solution. Electrochemical studies indicate that the catalyst is a water-soluble molecular species, that is among the most rapid homogeneous catalysts for water oxidation, with a turnover frequency of ∼81.54 s−1 (at pH 8.6, the lowest pH among those of any reported electrocatalysts) at an overpotential of 560 mV. 1 also can catalyze hydrogen evolution from water with a TOF of 376 mol of hydrogen per mole of catalyst per hour at an overpotential of 687.6 mV (pH 7.0). This is attributed to the planar ligand (bpbH2), that coordinates strongly through four nitrogen atoms to the cobalt center, leaving two Cl− ions in axial position and making the Cl− ion ionize in organic solvents or water, and can stabilize both the high and low oxidation states of cobalt well.

A dinuclear copper(II) electrocatalyst both water reduction and oxidation

Splitting water is a key challenge in the production of chemical fuels from electricity. Although several catalysts have been developed for these reactions, substantial challenges remain towards the ultimate goal of an efficient, inexpensive and robust electrocatalyst. Until now, there is as yet no report on both water oxidation and reduction by identical catalyst. Reported here is the first soluble copper-based catalyst, Cu(Me2oxpn)Cu(OH)2] 1 (Me2oxpn: N,N′-bis(2,2′-dimethyl-3-aminopropyl)oxamido) for both electrolytic water oxidation and reduction. Water oxidation occurs at an overpotential of 636 mV vs SHE to give O2 with a turnover frequency (TOF) of ∼2.14 s−1. Electrochemical studies also indicate that 1 is a soluble molecular species, that is among the most rapid homogeneous water reduction catalysts, with a TOF of 654 mol of hydrogen per mole of catalyst per hour at an overpotential of 789 mV vs SHE (pH 7.0). Sustained water reduction catalysis occurs at glassy carbon (GC) to give H2 over a 32 h electrolysis period with 95% Faradaic yield and no observable decomposition of the catalyst.

A mononuclear copper electrocatalyst for both water reduction and oxidation

The oxidation and reduction of water is a key challenge in the production of chemical fuels from electricity.

A soluble copper–bipyridine water-oxidation electrocatalyst

The oxidation of water to O(2) is a key challenge in the production of chemical fuels from electricity. Although several catalysts have been developed for this reaction, substantial challenges remain towards the ultimate goal of an efficient, inexpensive and robust electrocatalyst. Reported here is the first copper-based catalyst for electrolytic water oxidation. Copper-bipyridine-hydroxo complexes rapidly form in situ from simple commercially available copper salts and bipyridine at high pH. Cyclic voltammetry of these solutions at pH 11.8-13.3 shows large, irreversible currents, indicative of catalysis. The production of O(2) is demonstrated both electrochemically and with a fluorescence probe. Catalysis occurs at about 750 mV overpotential. Electrochemical, electron paramagnetic resonance and other studies indicate that the catalyst is a soluble molecular species, that the dominant species in the catalytically active solutions is (2,2'-bipyridine)Cu(OH)(2) and that this is among the most rapid homogeneous water-oxidation catalysts, with a turnover frequency of ~100 s(-1).