Methylation of Si(111) Modulates Molecular Orientation in Perylenediimide Thin Films.

Singlet fission produces a pair of low-energy spin-triplet excitons from a single high-energy spin-singlet exciton. While this process offers the potential to enhance the efficiency of silicon solar cells by ∼30%, meeting this goal requires overlayer materials that can efficiently transport triplet excitons to an underlying silicon substrate. Herein, we demonstrate that the chemical functionalization of silicon surfaces controls the structure of vapor-deposited thin films of perylenediimide (PDI) dyes, which are prototypical singlet fission materials.

Efficient photon upconversion enabled by strong coupling between silicon quantum dots and anthracene.

Hybrid structures formed between organic molecules and inorganic quantum dots can accomplish unique photophysical transformations by taking advantage of their disparate properties. The electronic coupling between these materials is typically weak, leading photoexcited charge carriers to spatially localize to the dot or to a molecule at its surface. However, we show that by converting a chemical linker that covalently binds anthracene molecules to silicon quantum dots from a carbon-carbon single bond to a double bond, we access a strong coupling regime where excited carriers spatially delocalize across both anthracene and silicon.

In Situ Analytical Techniques for the Investigation of Material Stability and Interface Dynamics in Electrocatalytic and Photoelectrochemical Applications.

Electrocatalysis and photoelectrochemistry are critical to technologies like fuel cells, electrolysis, and solar fuels. Material stability and interfacial phenomena are central to the performance and long-term viability of these technologies. Researchers need tools to uncover the fundamental processes occurring at the electrode/electrolyte interface.

Pulsed Electrochemical Carbon Monoxide Reduction on Oxide-Derived Copper Catalyst.

Efficient electroreduction of carbon dioxide has been a widely pursued goal as a sustainable method to produce value-added chemicals while mitigating greenhouse gas emissions. Processes have been demonstrated for the electroreduction of CO to CO at nearly 100 % faradaic efficiency, and as a consequence, there has been growing interest in the further electroreduction of carbon monoxide. Oxide-derived copper catalysts have promising performance for the reduction of CO to hydrocarbons but have still been unable to achieve high selectivity to individual products.

Exploiting Metal-Ligand Cooperativity to Sequester, Activate, and Reduce Atmospheric Carbon Dioxide with a Neutral Zinc Complex.

As atmospheric levels of carbon dioxide (CO) continue to increase, there is an immediate need to balance the carbon cycle. Current approaches require multiple processes to fix CO from the atmosphere or flue gas and then reduce it to value-added products. The zinc(II) catalyst Zn(DMTH) (DMTH = diacetyl-2-(4-methyl-3-thiosemicarbazonate)-3-(2-pyridinehydrazonato)) reduces CO from air to formate with a faradaic efficiency of 15.

Photocatalytic hydrogen evolution on Si photocathodes modified with bis(thiosemicarbazonato)nickel(ii)/Nafion.

The molecular catalyst diacetyl-bis(N-4-methyl-3-thiosemi-carbazonato)nickel(ii) (NiATSM) was integrated with Si for light-driven hydrogen evolution from water. Compared to an equivalent loading of Ni metal, the NiATSM/p-Si electrode performed better. Durability of the surface-bound catalyst under operation in acid was achieved without covalent attachment by using Nafion binding.