Opportunities and Challenges of Solar-Energy-Driven Carbon Dioxide to Fuel Conversion with Plasmonic Catalysts

Abstract

The ability of plasmonic nanoparticles to harness visible light can be being combined with their catalytic activity to drive photocatalytic transformations. This Review introduces the promise of this new class of photocatalysts for fulfilling the quest for sunlight-driven recycling of CO 2 into transportable liquid fuels. We discuss the prospects and challenges of such an approach. Despite considerable advances, a selective, stable, and efficient CO 2 reduction reaction (CO 2 RR) catalyst has been elusive. These open challenges may be addressable by the strategic utilization of plasmonic light excitation. Plasmonic catalysts have exhibited the ability to drive a rich milieu of CO 2 RR processes under visible light excitation. At this stage, improved mechanistic understanding and reaction control are needed. To motivate rational design of photocatalytic materials and processes by a future generation of researchers, we suggest potential pathways by which plasmonic-assisted CO 2 RR can take place. We describe unique physical and chemical aspects of plasmonic catalysis, some of which may allow modulation of CO 2 RR product selectivity in favor of higher hydrocarbons. The intertwining of the photophysics of plasmon resonances and chemistry of CO 2 RR creates a wide-open space for fundamental inquiry and technological development. Whether the future of artificial photosynthesis is "plasmonic" will be dictated by scientific understanding and engineering advances accomplished in the coming decade.

Emerging Applications of Plasmons in Driving CO2 Reduction and N2 Fixation

“…There is still a long way for researchers to push the efficiencies and selectivities of plasmon‐enhanced CO 2 reduction and N 2 fixation to the level of practical use. The exact understanding of the underlying plasmonic effects in photocatalysis is crucial for the rational design of efficient photocatalysts . We note that in the literature there have been reports where the role played by plasmons has been misunderstood.…”

“…The reduction potentials for various CO 2 reduction reactions under the standard conditions are shown in Figure a. The standard Gibbs free energy of formation for CO 2 is Δ G f ° = −394.4 kJ mol −1 , suggesting the high stability of CO 2 under standard conditions and its low propensity for conversion to reduced products . The rate‐determining step in CO 2 reduction is therefore thought to be the transfer of an electron to the CO 2 molecule.…”

“…The coupling between C 1 or other intermediates can result in the production of C 2+ hydrocarbons with more than one carbon atom in molecules, such as ethylene (CH 2 CH 2 ), ethane (C 2 H 6 ), and ethanol (C 2 H 5 OH). The higher hydrocarbons are favored in CO 2 reduction owing to their higher energy densities . Hydrocarbons in the liquid state are further favored as they are easy for transportation.…”

Design-controlled synthesis of IrO2 sub-monolayers on Au nanoflowers: marrying plasmonic and electrocatalytic properties

“…Plasmonic catalysis relies on harvesting the energy generated by localized surface plasmon resonant (LSPR) excitations in plasmonic nanoparticles to drive, accelerate, and/or control molecular transformations. [1][2][3][4][5][6] Following LSPR excitation in plasmonic nanoparticles, non-radiative plasmon decay can limited by significant efficiency loss and high overpotentials (η) as a result of the sluggish kinetics for the oxygen evolution reaction (OER, which represents the oxidative halfreaction). 32,33 It has been established that iridium and ruthenium oxides (IrO 2 and RuO 2 , respectively) are among the best OER electrocatalysts, and IrO 2 is often used in proton exchange membrane water electrolyzers as a result of its higher durability relative to RuO 2 .…”

Production of Higher Hydrocarbons from CO2 over Nanosized Iron Catalysts

“…Considerable work has been reported on catalytic hydrogenation of CO 2 to formic acid , , methanol , , syngas , and jet fuels using homogeneous and heterogeneous catalysts. From the thermodynamic and kinetic point of view, CO 2 conversion to long‐chain hydrocarbons and oxygenates is more challenging than to simple CO, CH 4 , HCOOH, and HCHO . These valuable liquid‐state fuels have higher energy density and are more convenient to store and transport.…”