The silver-mediated C–H trifluoromethylation of aromatic substrates using TMSCF3 is described. The development, optimization, and scope of these transformations are reported. AgCF3 intermediates are proposed.

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The inertness of the C–H bond in CH4 poses significant challenges to selective CH4 oxidation, which often proceeds all the way to CO2 once activated. Selective oxidation of CH4 to high-value industrial chemicals such as CO or CH3OH remains a challenge. Presently, the main methods to activate CH4 oxidation include thermochemical, electrochemical, and photocatalytic reactions. Of them, photocatalytic reactions hold great promise for practical applications but have been poorly studied. Existing demonstrations of photocatalytic CH4 oxidation exhibit limited control over the product selectivity, with CO2 as the most common product. The yield of CO or other hydrocarbons is too low to be of any practical value. In this work, we show that highly selective production of CO by CH4 oxidation can be achieved by a photoelectrochemical (PEC) approach. Under our experimental conditions, the highest yield for CO production was 81.9%. The substrate we used was TiO2 grown by atomic layer deposition (ALD), which features high concentrations of Ti3+ species. The selectivity toward CO was found to be highly sensitive to the substrate types, with significantly lower yield on P25 or commercial anatase TiO2 substrates. Moreover, our results revealed that the selectivity toward CO also depends on the applied potentials. Based on the experimental results, we proposed a reaction mechanism that involves synergistic effects by adjacent Ti sites on TiO2. Spectroscopic characterization and computational studies provide critical evidence to support the mechanism. Furthermore, the synergistic effect was found to parallel heterogeneous CO2 reduction mechanisms. Our results not only present a new route to selective CH4 oxidation, but also highlight the importance of mechanistic understandings in advancing heterogeneous catalysis.

We report CF 3 -substituted porphyrins and evaluate their use as photosensitizers in water-splitting dyesensitized photoelectrochemical cells (WS-DSPECs) by characterizing interfacial electron transfer on metal oxide surfaces. By using (CF 3 ) 2 C 6 H 3 instead of C 6 F 5 substituents at the meso positions, we obtain the desired high potentials while avoiding the sensitivity of C 6 F 5 substituents to nucleophilic substitution, a process that limits the types of synthetic reactions that can be used. Both the number of CF 3 groups and the central metal tune the ground and excited-state potentials. A pair of porphyrins bearing carboxylic acids as anchoring groups were deposited on SnO 2 and TiO 2 surfaces, and the interfacial charge-injection and charge-recombination kinetics were characterized by using a combination of computational modeling, terahertz measurements, and transient absorption spectroscopy. We find that both free-base and metalated porphyrins inject into SnO 2 and that recombination is slower for the latter case. These findings demonstrate that (CF 3 ) 2 C 6 H 3 -substituted porphyrins are promising photosensitizers for use in WS-DSPECs.

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