Engendering Long-Term Air and Light Stability of a TiO₂‑Supported Porphyrinic Dye via Atomic Layer Deposition

Organic and porphyrin-based chromophores are prevalent in liquid-junction photovoltaic and photocatalytic solar-cell chemistry; however, their long-term air and light instability may limit their practicality in real world technologies. Here, we describe the protection of a zinc porphyrin dye, adsorbed on nanoparticulate TiO₂, from air and light degradation by a protective coating of alumina grown with a previously developed post-treatment atomic layer deposition (ALD) technique. The protective Al₂O₃ ALD layer is deposited using dimethylaluminum isopropoxide as an Al source; in contrast to the ubiquitous ALD precursor trimethylaluminum, dimethylaluminum isopropoxide does not degrade the zinc porphyrin dye, as confirmed by UV–vis measurements. The growth of this protective ALD layer around the dye can be monitored by an in-reactor quartz crystal microbalance (QCM). Furthermore, greater than 80% of porphyrin light absorption is retained over ∼1 month of exposure to air and light when the protective coating is present, whereas almost complete loss of porphyrin absorption is observed in less than 2 days in the absence of the ALD protective layer. Applying the Al₂O₃ post-treatment technique to the TiO₂-adsorbed dye allows the dye to remain in electronic contact with both the semiconductor surface and a surrounding electrolyte solution, the combination of which makes this technique promising for numerous other electrochemical photovoltaic and photocatalytic applications, especially those involving the dye-sensitized evolution of oxygen

Atomic Layer Deposition of Ultrathin Nickel Sulfide Films and Preliminary Assessment of Their Performance as Hydrogen Evolution Catalysts

Transition metal sulfides show great promise for applications ranging from catalysis to electrocatalysis to photovoltaics due to their high stability and conductivity. Nickel sulfide, particularly known for its ability to electrochemically reduce protons to hydrogen gas nearly as efficiently as expensive noble metals, can be challenging to produce with certain surface site compositions or morphologies, e.g., conformal thin films. To this end, we employed atomic layer deposition (ALD), a preeminent method to fabricate uniform and conformal films, to construct thin films of nickel sulfide (NiS_<i>x</i>) using bis­(<i>N</i>,<i>N</i>′-di-<i>tert</i>-butyl­acetamidinato)­nickel­(II) (Ni­(amd)₂) vapor and hydrogen sulfide gas. Effects of experimental conditions such as pulse and purge times and temperature on the growth of NiS_<i>x</i> were investigated. These revealed a wide temperature range, 125–225 °C, over which self-limiting NiS_<i>x</i> growth can be observed. <i>In situ</i> quartz crystal microbalance (QCM) studies revealed conventional linear growth behavior for NiS_<i>x</i> films, with a growth rate of 9.3 ng/cm² per cycle being obtained. The ALD-synthesized films were characterized using X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) methods. To assess the electrocatalyitic activity of NiS_<i>x</i> for evolution of molecular hydrogen, films were grown on conductive-glass supports. Overpotentials at a current density of 10 mA/cm² were recorded in both acidic and pH 7 phosphate buffer aqueous reaction media and found to be 440 and 576 mV, respectively, with very low NiS_<i>x</i> loading. These results hint at the promise of ALD-grown NiS_<i>x</i> materials as water-compatible electrocatalysts

Photodriven Oxidation of Surface-Bound Iridium-Based Molecular Water-Oxidation Catalysts on Perylene-3,4-dicarboximide-Sensitized TiO₂ Electrodes Protected by an Al₂O₃ Layer

Improving stability and slowing charge recombination are some of the greatest challenges in the development of dye-sensitized photoelectrochemical cells (DSPECs) for solar fuels production. We have investigated the effect of encasing dye molecules in varying thicknesses of Al₂O₃ deposited by atomic layer deposition (ALD) before catalyst loading on both the stability and the charge transfer dynamics in organic dye-sensitized TiO₂ photoanodes containing iridium-based molecular water-oxidation catalysts. In the TiO₂|dye|Al₂O₃|catalyst electrodes, a sufficiently thick ALD layer protects the perylene-3,4-dicarboximide (PMI) chromophores from degradation over several weeks of exposure to light. The insulating capacity of the layer allows a higher photocurrent in the presence of ALD while initial charge injection is slowed by only 1.6 times, as observed by femtosecond transient absorption spectroscopy. Rapid picosecond-scale catalyst oxidation is observed in the presence of a dinuclear catalyst, IrIr, but is slowed to tens of picoseconds for a mononuclear catalyst, IrSil, that incorporates a long linker. Photoelectrochemical experiments demonstrate higher photocurrents with IrSil compared to IrIr, which show that recombination is slower for IrSil, while higher photocurrents with IrIr upon addition of ALD layers confirm that ALD successfully slows charge recombination. These findings demonstrate that, beyond stability improvements, ALD can contribute to tuning charge transfer dynamics in photoanodes for solar fuels production and may be particularly useful for slowing charge recombination and accounting for varying charge transfer rates based on the molecular structures of incorporated catalysts

Highly Active NiO Photocathodes for H₂O₂ Production Enabled via Outer-Sphere Electron Transfer

Tandem dye-sensitized photoelectrosynthesis cells are promising architectures for the production of solar fuels and commodity chemicals. A key bottleneck in the development of these architectures is the low efficiency of the photocathodes, leading to small current densities. Herein, we report a new design principle for highly active photocathodes that relies on the outer-sphere reduction of a substrate from the dye, generating an unstable radical that proceeds to the desired product. We show that the direct reduction of dioxygen from dye-sensitized nickel oxide (NiO) leads to the production of H₂O₂. In the presence of oxygen and visible light, NiO photocathodes sensitized with commercially available porphyrin, coumarin, and ruthenium dyes exhibit large photocurrents (up to 400 μA/cm²) near the thermodynamic potential for O₂/H₂O₂ in near-neutral water. Bulk photoelectrolysis of porphyrin-sensitized NiO over 24 h results in millimolar concentrations of H₂O₂ with essentially 100% faradaic efficiency. To our knowledge, these are among the most active NiO photocathodes reported for multiproton/multielectron transformations. The photoelectrosynthesis proceeds by initial formation of superoxide, which disproportionates to H₂O₂. This disproportionation-driven charge separation circumvents the inherent challenges in separating electron–hole pairs for photocathodes tethered to inner sphere electrocatalysts and enables new applications for photoelectrosynthesis cells