Earth-Abundant Molecular Z-Scheme Photoelectrochemical Cell for Overall Water-Splitting.

A push-pull organic dye and a cobaloxime catalyst were successfully cografted on NiO and CuGaO2 to form efficient molecular photocathodes for H2 production with >80% Faradaic efficiency. CuGaO2 is emerging as a more effective p-type semiconductor in photoelectrochemical cells and yields a photocathode with 4-fold higher photocurrent densities and 400 mV more positive onset photocurrent potential compared to the one based on NiO. Such an optimized CuGaO2 photocathode was combined with a TaON|CoO x photoanode in a photoelectrochemical cell. Operated in this Z-scheme configuration, the two photoelectrodes produced H2 and O2 from water with 87% and 88% Faradaic efficiency, respectively, at pH 7 under visible light and in the absence of an applied bias, equating to a solar to hydrogen conversion efficiency of 5.4 × 10-3%. This is, to the best of our knowledge, the highest efficiency reported so far for a molecular-based noble metal-free water splitting Z-scheme.

On the Use of Metal Sinter Powder in Laser Powder Bed Fusion Processing (PBF-LB/M).

Metal Laser Powder Bed Fusion (PBF-LB/M Powder Bed Fusion, Laser-Based/Metal) offers decisive advantages over conventional manufacturing processes. Complex geometries can be produced that cannot, or only to a limited extent, be manufactured with conventional manufacturing processes. One of the main disadvantages of the process are high investment and operating costs. In order to make the PBF-LB/M process accessible to new research areas, the costs need to be reduced. Therefore, this work investigates whether laser beam sources and motion systems in currently established PBF-LB/M systems can be replaced by more cost-effective components. To reduce the operating costs for PBF-LB/M, the studies are carried out based on previous work with water-atomized, process-foreign sinter powder instead of gas-atomized, spherical PBF-LB/M powders. A cost-efficient, low-alloyed powder is selected (Höganäs HP1) and processed on two different PBF-LB/M machines with a restricted process window using process parameter values that current low-cost machines can achieve. The results show that a multimode fiber laser leads to a more stable process and wider melt pools compared to a single mode fiber laser. In addition, a lower sensitivity of the process with respect to modified process parameters is observed for the multimode laser, resulting in a wider range of stable process windows. A Cartesian motion system (gantry) is suitable for use in PBF-LB/M despite lower scan speeds compared to galvanometer scanners. Beam guidance in the XY-plane offers new possibilities for machine and process design that are not possible with usual scanner systems.

Localizing the initial excitation - A case study on NiO photocathodes using Ruthenium dipyridophenazine complexes as sensitizers.

We report on the localization of the initially excited electronic state within the molecular framework of a series of [Ru(bpy)2dppz]2+ derivatives (bpy:2,2'-bipyridine, dppz: dipyrido-phenazine) as sensitizers in NiO based photocathodes. The introduction of conjugated linkers with phenylene and triazole moieties in the bpy ligand sphere separates the NiO surface from the metal center and hence is considered to stabilize the charge separated state, which results from light-driven hole injection. However, introduction of the conjugated linkers also alters the localization of the excess electron density in the excited state within the ligand sphere and impacts the extent to which the charge-separated state is formed. The study emphasizes that tuning the ligand with the lowest-energy π* orbital distal or proximal to the NiO surface significantly affects the initial charge-separation and the solar cell performance. The stability of the charge-separated state correlates with the observed photocurrents in dye-sensitized solar cells. Furthermore, the study challenges the widely accepted concept that the introduction of extended anchoring groups, i.e. increasing Ru - NiO distance, stabilizes the charge-separated state and suppresses charge recombination at the metal-oxide molecule interface.

Photocathodes beyond NiO: charge transfer dynamics in a π-conjugated polymer functionalized with Ru photosensitizers.

A conductive polymer (poly(p-phenylenevinylene), PPV) was covalently modified with RuII complexes to develop an all-polymer photocathode as a conceptual alternative to dye-sensitized NiO, which is the current state-of-the-art photocathode in solar fuels research. Photocathodes require efficient light-induced charge-transfer processes and we investigated these processes within our photocathodes using spectroscopic and spectro-electrochemical techniques. Ultrafast hole-injection dynamics in the polymer were investigated by transient absorption spectroscopy and charge transfer at the electrode-electrolyte interface was examined with chopped-light chronoamperometry. Light-induced hole injection from the photosensitizers into the PPV backbone was observed within 10 ps and the resulting charge-separated state (CSS) recombined within ~ 5 ns. This is comparable to CSS lifetimes of conventional NiO-photocathodes. Chopped-light chronoamperometry indicates enhanced charge-transfer at the electrode-electrolyte interface upon sensitization of the PPV with the RuII complexes and p-type behavior of the photocathode. The results presented here show that the polymer backbone behaves like classical molecularly sensitized NiO photocathodes and operates as a hole accepting semiconductor. This in turn demonstrates the feasibility of all-polymer photocathodes for application in solar energy conversion.

Hydrogen Production at a NiO Photocathode Based on a Ruthenium Dye-Cobalt Diimine Dioxime Catalyst Assembly: Insights from Advanced Spectroscopy and Post-operando Characterization.

The production of hydrogen by efficient, low-cost, and integrated photoelectrochemical water splitting processes represents an important target for the ecological transition. This challenge can be addressed thanks to bioinspired chemistry and artificial photosynthesis approaches by designing dye-sensitized photocathodes for hydrogen production, incorporating bioinspired first-row transition metal-based catalysts. The present work describes the preparation and photoelectrochemical characterization of a NiO photocathode sensitized with a phosphonate-derivatized ruthenium tris-diimine photosensitizer covalently linked to a cobalt diimine dioxime hydrogen-evolving catalyst. Under simulated AM 1.5G irradiation, hydrogen is produced with photocurrent densities reaching 84 ± 7 µA·cm-2, which is among the highest values reported so far for dye-sensitized photocathodes with surface-immobilized catalysts. Thanks to the unique combination of advanced spectroscopy and surface characterization techniques, the fast desorption of the dyad from the NiO electrode and the low yield of electron transfer to the catalyst, resulting in the Co demetallation from the diimine dioxime framework, were identified as the main barriers limiting the performances and the stability of the system. This work therefore paves the way for a more rational design of molecular photocathodes for solar fuel production and represents a further step toward the development of sustainable processes for the production of hydrogen from sunlight and water.

Electron transfer in a covalent dye-cobalt catalyst assembly - a transient absorption spectroelectrochemistry perspective.

Various oxidation states of the catalytically active cobalt center in a covalent dyad were electrochemically prepared and the light-induced excited-state processes were studied. Virtually identical deactivation processes are observed, irrespective of the oxidation state of the cobalt center, varying from CoIII to CoI, indicating the absence of oxidative quenching within the dye-catalyst assembly.