RESUMEN
Renewable electricity powered electrochemical CO2 reduction (CO2R) offers a valuable method to close the carbon cycle and reduce our overreliance on fossil fuels. However, high purity CO2 is usually required as feedstock, which potentially decreases the feasibility and economic viability of the process. Direct conversion of flue gas is an attractive option but is challenging due to the low CO2 concentration and the presence of O2 impurities. As a result, up to 99% of the applied current can be lost towards the undesired oxygen reduction reaction (ORR). Here, we show that acidic electrolyte can significantly suppress ORR on Cu, enabling generation of multicarbon products from simulated flue gas. Using a composite Cu and carbon supported single-atom Ni tandem electrocatalyst, we achieved a multicarbon Faradaic efficiency of 46.5% at 200 mA cm-2, which is ~20 times higher than bare Cu under alkaline conditions. We also demonstrate stable performance for 24 h with a multicarbon product full-cell energy efficiency of 14.6%. Strikingly, this result is comparable to previously reported acidic CO2R systems using pure CO2. Our findings demonstrate a potential pathway towards designing efficient electrolyzers for direct conversion of flue gas to value-added chemicals and fuels.
RESUMEN
Tuning interfacial electric fields provides a powerful means to control electrocatalyst activity. Importantly, electric fields can modify adsorbate binding energies based on their polarizability and dipole moment, and hence operate independently of scaling relations that fundamentally limit performance. However, implementation of such a strategy remains challenging because typical methods modify the electric field non-uniformly and affects only a minority of active sites. Here we discover that uniformly tunable electric field modulation can be achieved using a model system of single-atom catalysts (SACs). These consist of M-N4 active sites hosted on a series of spherical carbon supports with varying degrees of nanocurvature. Using in-situ Raman spectroscopy with a Stark shift reporter, we demonstrate that a larger nanocurvature induces a stronger electric field. We show that this strategy is effective over a broad range of SAC systems and electrocatalytic reactions. For instance, Ni SACs with optimized nanocurvature achieved a high CO partial current density of ~400 mA cm-2 at >99% Faradaic efficiency for CO2 reduction in acidic media.
RESUMEN
Electrochemical CO2 reduction (CO2 R) in acidic media with Cu-based catalysts tends to suffer from lowered selectivity towards multicarbon products. This could in principle be mitigated using tandem catalysis, whereby the *CO coverage on Cu is increased by introducing a CO generating catalyst (e.g. Ag) in close proximity. Although this has seen significant success in neutral/alkaline media, here we report that such a strategy becomes impeded in acidic electrolyte. This was investigated through the co-reduction of 13 CO2 /12 CO mixtures using a series of Cu and CuAg catalysts. These experiments provide strong evidence for the occurrence of tandem catalysis in neutral media and its curtailment under acidic conditions. Density functional theory simulations suggest that the presence of H3 O+ weakens the *CO binding energy of Cu, preventing effective utilization of tandem-supplied CO. Our findings also provide other unanticipated insights into the tandem catalysis reaction pathway and important design considerations for effective CO2 R in acidic media.
