RESUMO
Solar-fuel formation via photoelectrochemical (PEC) routes using water and CO2 as feedstock has attracted much attention. Most PEC CO2 reduction studies have been focused on the development of novel photoactive materials; however, there is still a lack of understanding of the key limiting factors of this process. In this study, the theoretical limits of Solar-to-Fuel (STF) efficiencies of single- and dual-junction photo-absorbing materials are illustrated for single-step multi-electron CO2 reduction into fuels including HCOO- , CO, CH3 OH and C2 H5 OH. It is also highlighted that STF efficiency depends on the route of two-step PEC CO2 reduction process using CH3 OH as a model fuel. Finally, it is illustrated the beneficial role of alternative strategies such as dual-junction photo-absorbing electrodes, externally applied bias and subsequent reactor chambers on the maximum theoretical efficiencies of PEC CO2 reduction.
RESUMO
Utilising photoelectrochemical (PEC) devices to produce sustainable fuels from water and CO2 is a very attractive strategy, in which sunlight is used to convert the greenhouse gas (CO2) into a usable form of stored chemical energy. While significant progress has been made in the development of efficient photoactive catalysts for PEC reactions, limited efforts have been focused on the reactor design where continuous flow microfluidic PEC reactors are particular promising. In this work, a range of CuO-based thin films were used as photocathodes in a continuous flow microfluidic PEC reactor using CO2-saturated aqueous NaHCO3 solution under simulated AM 1.5 solar irradiation for up to 12 h. The highest photocurrent density obtained was for the α-Fe2O3/CuO photoelectrode yielding -1.0 mA cm-2 at 0.3 V vs. RHE and initial results indicated a solar-to-fuel (STF) efficiency of 0.48%. While the CuO, Cu2O and CuO-Cu2O photoelectrodes virtually only formed formate, the bilayer α-Fe2O3/CuO photocathode produced methanol in addition to formate indicating that combined copper and iron oxides in continuous flow microfluidic PEC cells have great potential of direct solar conversion into useful chemicals.
RESUMO
Hybrid redox flow cells (HRFC) are key enablers for the development of reliable large-scale energy storage systems; however, their high cost, limited cycle performance, and incompatibilities associated with the commonly used carbon-based electrodes undermine HRFC's commercial viability. While this is often linked to lack of suitable electrocatalytic materials capable of coping with HRFC electrode processes, the combinatory use of nanocarbon additives and carbon paper electrodes holds new promise. Here, by coupling electrophoretically deposited nitrogen-doped graphene (N-G) with carbon electrodes, their surprisingly beneficial effects on three types of HRFCs, namely, hydrogen/vanadium (RHVFC), hydrogen/manganese (RHMnFC), and polysulfide/air (S-Air), are revealed. RHVFCs offer efficiencies over 70% at a current density of 150 mA cm-2 and an energy density of 45 Wh L-1 at 50 mA cm-2, while RHMnFCs achieve a 30% increase in energy efficiency (at 100 mA cm-2). The S-Air cell records an exchange current density of 4.4 × 10-2 mA cm-2, a 3-fold improvement of kinetics compared to the bare carbon paper electrode. We also present cost of storage at system level compared to the standard all-vanadium redox flow batteries. These figures-of-merit can incentivize the design, optimization, and adoption of high-performance HRFCs for successful grid-scale or renewable energy storage market penetration.