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Photoelectrochemical fuel generation is a promising route to sustainable liquid fuels produced from water and captured carbon dioxide with sunlight as the energy input. Development of these technologies requires photoelectrode materials that are both photocatalytically active and operationally stable in harsh oxidative and/or reductive electrochemical environments. Such photocatalysts can be discovered based on co-design principles, wherein design for stability is based on the propensity for the photocatalyst to self-passivate under operating conditions and design for photoactivity is based on the ability to integrate the photocatalyst with established semiconductor substrates. Here, we report on the synthesis and characterization of zinc titanium nitride (ZnTiN2) that follows these design rules by having a wurtzite-derived crystal structure and showing self-passivating surface oxides created by electrochemical polarization. The sputtered ZnTiN2 thin films have optical absorption onsets below 2 eV and n-type electrical conduction of 3 S/cm. The band gap of this material is reduced from the 3.36 eV theoretical value by cation-site disorder, and the impact of cation antisites on the band structure of ZnTiN2 is explored using density functional theory. Under electrochemical polarization, the ZnTiN2 surfaces have TiO2- or ZnO-like character, consistent with Materials Project Pourbaix calculations predicting the formation of stable solid phases under near-neutral pH. These results show that ZnTiN2 is a promising candidate for photoelectrochemical liquid fuel generation and demonstrate a new materials design approach to other photoelectrodes with self-passivating native operational surface chemistry.

Sustainable production of liquid fuels from abundant resources, such as carbon dioxide and water, may be possible through photoelectrochemical processes. Zinc titanium nitride (ZnTiN2) has been recently demonstrated as a potential photoelectrode semiconductor for photoelectrochemical fuel generation due to its ideal bandgap induced by cation disorder, shared crystal structure with established semiconductors, and self-passivating surface oxides under carbon dioxide reduction operating conditions. However, substantial improvements in crystalline quality and optoelectronic properties of ZnTiN2 are needed to enable such applications. In this work, we investigate the heteroepitaxial growth of ZnTiN2 on c-plane (001) sapphire substrates. Growth on sapphire improves crystal quality, while growth on sapphire at elevated temperatures (300 °C) yields highly-oriented, single-crystal-like ZnTiN2 films. When Sn is incorporated during these epitaxial growth conditions, notable improvements in ZnTiN2 film surface roughness and optoelectronic properties are observed. These improvements are attributed to Sn acting as a surfactant during growth and mitigating unintentional impurities such as O and C. The single-crystal-like, 12% Sn-containing ZnTiN2 films exhibit a steep optical absorption onset at the band gap energy around 2 eV, electrical resistivity of 0.7 Ω cm, and a carrier mobility of 0.046 cm2 V−1 s−1 with n-type carrier concentration of 2 × 1020 cm−3. Density functional theory calculations reveal that moderate substitution of Sn (12.5% of the cation sites) on energetically-preferred cation sites has negligible impact on the optoelectronic properties of cation-disordered ZnTiN2. These results are important steps toward achieving high performance PEC devices based on ZnTiN2 photoelectrodes with efficient photon absorption and photoexcited carrier extraction. [ABSTRACT FROM AUTHOR]

The rate of singlet fission, the process of generating two triplet excitons with photoexcitation of one singlet exciton, depends on a combination of singlet/triplet energy balance and intermolecular coupling. Here, we perform carboxylic acid functionalization of anthradithiophene (ADT) derivatives that results in hydrogen bonds that drive molecular orientation and strong electronic coupling of polycrystalline ADT thin films, leading to ultrafast singlet fission without significant enthalpic driving force. ADT with a single carboxylic acid group exhibits weak intermolecular coupling and slow and inefficient singlet fission, much like the parent ADT, and substitution of different alkylsilyl solubilizing groups has little effect. However, the addition of two carboxylic acid groups on either end of the long axis favors significant coupling and crystallinity in as‐deposited thin films that increase the effective singlet fission rate by roughly three orders of magnitude. The properties of the triplet pair, particularly its propensity to form long‐lived independent triplets, are also influenced by the degree of long‐range intermolecular coupling. The enhancement of intermolecular coupling specific to singlet fission using the ubiquitous cyclic hydrogen bonding motif could impact triplet pair utilization schemes in a variety of contexts. [ABSTRACT FROM AUTHOR]

Interfacial electron transfer at titanium dioxide (TiO2) is investigated for a series of surface bound ruthenium-polypyridyl dyes whose metal-to-ligand charge-transfer state (MLCT) energetics are tuned through chemical modification. The 12 complexes are of the form RuII(bpy-A)(L)22+, where bpy-A is a bipyridine ligand functionalized with phosphonate groups for surface attachment to TiO2. Functionalization of ancillary bipyridine ligands (L) enables the potential of the excited state RuIII/*couple, E+/*, in 0.1 M perchloric acid (HClO4(aq)) to be tuned from -0.69 to -1.03 V vs NHE. Each dye is excited by a 200 fs pulse of light in the visible region of the spectrum and probed with a time-delayed supercontiuum pulse (350-800 nm). Decay of the MLCT excited-state absorption at 376 nm is observed without loss of the ground-state bleach, which is a clear signature of electron injection and formation of the oxidized dye. The dye-dependent decays are biphasic with time constants in the 3-30 and 30-500 ps range. The slower injection rate constant for each dye is exponentially distributed relative to E+/*. The correlation between the exponentially diminishing density of TiO2 sub-band acceptor levels and injection rate is well described using Marcus-Gerischer theory, with the slower decay components being assigned to injection from the thermally equilibrated state and the faster components corresponding to injection from higher energy states within the 3MLCT manifold. These results and detailed analyses incorporating molecular photophysics and semiconductor density of states measurements indicate that the multiexponential behavior that is often observed in interfacial injection studies is not due to sample heterogeneity. Rather, this work shows that the kinetic heterogeneity results from competition between excited-state relaxation and injection as the photoexcited dye relaxes through the 3MLCT manifold to the thermally equilibrated state, underscoring the potential for a simple kinetic model to reproduce the complex kinetic behavior often observed at the interface of mesoporous metal oxide materials. [ABSTRACT FROM AUTHOR]

Singlet fission, the process of transforming a singlet excited state into two lower energy triplet excited states, is a promising strategy for improving the efficiency of dye-sensitized solar cells. The difficulty in utilizing singlet fission molecules in this architecture is understanding and controlling the orientation of dyes on mesoporous metal oxide surfaces to maximize triplet production and minimize detrimental deactivation pathways, such as electron injection from the singlet or excimer formation. Here, we varied the concentration of loading solutions of two anthradithiophene dyes derivatized with either one or two carboxylic acid groups for binding to a metal oxide surface and studied their photophysics using ultrafast transient absorption spectroscopy. For the single carboxylic acid case, an increase in dye surface coverage led to an increase in apparent triplet excited-state growth via singlet fission, while the same increase in coverage with two carboxylic acids did not. This study represents a step toward controlling the interactions between molecules at mesoporous interfaces., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

2,2'-Bis(4-dimethylaminophenyl)- and 2,2'-dicyclohexyl-1,1',3,3'-tetramethyl-2,2',3,3'-tetrahydro-2,2'-bibenzo[ d ]imidazole ((N-DMBI) 2 and (Cyc-DMBI) 2 ) are quite strong reductants with effective potentials of ca. -2 V vs ferrocenium/ferrocene, yet are relatively stable to air due to the coupling of redox and bond-breaking processes. Here, we examine their use in accomplishing electron transfer-induced bond-cleavage reactions, specifically dehalogenations. The dimers reduce halides that have reduction potentials less cathodic than ca. -2 V vs ferrocenium/ferrocene, especially under UV photoexcitation (using a 365 nm LED). In the case of benzyl halides, the products are bibenzyl derivatives, whereas aryl halides are reduced to the corresponding arenes. The potentials of the halides that can be reduced in this way, quantum-chemical calculations, and steady-state and transient absorption spectroscopy suggest that UV irradiation accelerates the reactions via cleavage of the dimers to the corresponding radical monomers., (Copyright © 2023, Tang et al.)

Interfacial dynamics are investigated in SnO 2 /TiO 2 core/shell films derivatized with a Ru(II)-polypyridyl chromophore ([Ru II (bpy) 2 (4,4'-(PO 3 H 2 ) 2 bpy)] 2+ , RuP) using transient absorption methods. Electron injection from the chromophore into the TiO 2 shell occurs within a few picoseconds after photoexcitation. Loss of the oxidized dye through recombination occurs across time scales spanning 10 orders of magnitude. The majority (60%) of charge recombination events occur shortly after injection (τ = 220 ps), while a small fraction (≤20%) of the oxidized chromophores persists for milliseconds. The lifetime of long-lived charge-separated states (CSS) depends exponentially on shell thickness, suggesting that the injected electrons reside in the SnO 2 core and must tunnel through the TiO 2 shell to recombine with oxidized dyes. While the core/shell architecture extends the lifetime in a small fraction of the CSS, making water oxidation possible, the subnanosecond recombination process has profound implications for the overall efficiencies of dye-sensitized photoelectrosynthesis cells (DSPECs).