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At least 883 records · Page 49

Mechanistic Insights into Co and Fe Quaterpyridine-Based CO 2 Reduction Catalysts: Metal–Ligand Orbital Interaction as the Key Driving Force for Distinct Pathways

Both [Co II (qpy)(H 2 O) 2 ] 2+ and [Fe II (qpy)(H 2 O) 2 ] 2+ (with qpy = 2,2':6',2'':6'',2'''-quaterpyridine) are efficient homogeneous electrocatalysts and photoelectrocatalysts for the reduction of CO 2 to CO. The Co catalyst is more efficient in the electrochemical reduction, while the Fe catalyst is an excellent photoelectrocatalyst. This work uses density functional theory to shed light on the contrasting catalytic pathways. While both catalysts experience primarily ligand-based reductions, the second reduction in the Co catalyst is delocalized onto the metal via a metal-ligand bonding interaction, causing a spin transition and a distorted ligand framework. This orbital interaction explains the experimentally observed mild reduction potential and slow kinetics of the second reduction. The decreased hardness and doubly occupied d z 2 -orbital facilitate a σ-bond with the CO 2 -π* in an η 1 - κC binding mode. CO 2 binding is only possible after two reductions resulting in an EEC mechanism (E = electron transfer, C = chemical reaction), and the second protonation is rate-limiting. In contrast, the Fe catalyst maintains a Lewis acidic metal center throughout the reduction process because the metal orbitals do not strongly mix with the qpy-π* orbitals. Further, this allows binding of the activated CO 2 in an η 2 -binding mode. This interaction stabilizes the activated CO 2 via a π-type interaction of a Fe-t 2g orbital and the CO 2 -π* and a dative bond of the oxygen lone pair. This facilitates CO 2 binding to a singly reduced catalyst resulting in an ECE mechanism. The barrier for CO 2 addition and the second protonation are higher than those for the Co catalyst and rate-limiting.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tropical Cyclone Precipitation Response to Surface Warming in Aquaplanet Simulations With Uniform Thermal Forcing

While many modeling studies have attempted to estimate how tropical cyclone (TC) precipitation is impacted by climate change, the multitude of analysis techniques and methodologies have resulted in varying conclusions. Simplified models may be able to help overcome this problem. Radiative-convective equilibrium (RCE) model simulations have been used in various configurations to study fundamental aspects of Earth's climate. While many RCE modeling studies have focused on TC genesis, intensification, and size, limited work has been done using RCE to study TC precipitation. Here, in this study, the response of TC precipitation to sea surface temperature (SST) change is analyzed in global Community Atmosphere Model (CAM) aquaplanet simulations run with Radiative-Convective Equilibrium Model Intercomparison Project protocols, with the addition of planetary rotation. We expect that the insight gained about how TC precipitation responds to SST warming will help predict how TCs in the real world respond to climate change. In the CAM RCE simulations, the warmer SST simulations have less TCs on average, but the TCs tend to be larger in outer size and more intense. As simulation SST increases, more extreme precipitation rates occur within TCs, and more of the TC precipitation comes from these extreme rates. For extreme (99th percentile) TC precipitation, SST, and TC intensity increases dominate the 8.6% per K increase, while TC outer size changes have little impact. For accumulated TC precipitation, SST, and TC intensity contributions are still the majority, but TC outer size changes also contribute to the 6.6% per K increase.

54 ENVIRONMENTAL SCIENCES↗