Unraveling Sequential Oxidation Kinetics and Determining Roles of Multi-Cobalt Active Sites on Co3O4 Catalyst for Water Oxidation.

The multi-redox mechanism involving multi-sites has great implications to dictate the catalytic water oxidation. Understanding the sequential dynamics of multi-steps in oxygen evolution reaction (OER) cycles on working catalysts is a highly important but challenging issue. Here, using quasi-operando transient absorption (TA) spectroscopy and a typical photosensitization strategy, we succeeded in resolving the sequential oxidation kinetics involving multi-active sites for water oxidation in OER catalytic cycle, with Co3O4 nanoparticles as model catalysts. When OER initiates from fast oxidation of surface Co2+ ions, both surface Co2+ and Co3+ ions are active sites of the multi-cobalt centers for water oxidation. In the sequential kinetics (Co2+ → Co3+ → Co4+), the key characteristic is fast oxidation and slow consumption for all the cobalt species. Due to this characteristic, the Co4+ intermediate distribution plays a determining role in OER activity and results in the slow overall OER kinetics. These insights shed light on the kinetic understanding of water oxidation on heterogeneous catalysts with multi-sites.

Triplet Sensitization by "Self-Trapped" Excitons of Nontoxic CuInS2 Nanocrystals for Efficient Photon Upconversion.

Triplet energy transfer (TET) from semiconductor nanocrystals (NCs) has recently emerged as a new triplet sensitization paradigm. It remains unclear how trap states pervasive in NCs influence TET or whether trapped excitons can undergo efficient TET. Here we partially address this issue by studying TET from CuInS2 NCs as a model system because their photogenerated excitons are known to be "self-trapped" due to hole localization to intragap Cu states. We found that, thanks to the long lifetime (209 ± 17 ns) of self-trapped excitons, they could be extracted with an efficiency of ∼92.3% by surface-anchored anthracene despite that the TET rate was relatively slow (57.1 ± 1.7 µs-1). We further leveraged this efficient sensitization to achieve triplet-triplet-annihilation photon upconversion (TTA-UC) with a quantum yield of 18.6 ± 0.3%. Thus, this study not only demonstrates trapped excitons can undergo efficient TET as well, but also presents the first TTA-UC system sensitized by nontoxic NCs which is important for the real-life application of this technique.