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The use of cobalt porphyrin complexes as efficient and cost-effective molecular catalysts for water oxidation has been investigated previously. However, by combining a set of analytical techniques (electrochemistry, ultraviolet–visible spectroscopy (UV–vis), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and synchrotron-based photoelectron spectroscopy (SOXPES and HAXPES)), we have demonstrated that three different cobalt porphyrins, deposited on FTO glasses, decompose promptly into a thin film of CoOx on the surface of the electrode during water oxidation under certain conditions (borate buffer pH 9.2). It is presumed that the film is composed of CoO, only detectable by SOXPES, as conventional techniques are ineffective. This newly formed film has a high turnover frequency (TOF), while the high transparency of the CoOx-based electrode is very promising for future application in photoelectrochemical cells.

The development of a highly active manganese-based water oxidation catalyst in the design of an ideal artificial photosynthetic device operating under neutral pH conditions remains a great challenge, due to the instability of pivotal Mn3+ intermediates. We report here defective and “c-disordered” layered manganese oxides (MnO x -300) formed on a fluorine-doped tin oxide electrode by constant anodic potential deposition and subsequent annealing, with a catalytic onset (0.25 mA/cm2) at an overpotential (η) of 280 mV and a benchmark catalytic current density of 1.0 mA/cm2 at an overpotential (η) of 330 mV under neutral pH (1 M potassium phosphate). Steady current density above 8.2 mA/cm2 was obtained during the electrolysis at 1.4 V versus the normal hydrogen electrode for 20 h. Insightful studies showed that the main contributing factors for the observed high activity of MnO x -300 are (i) a defective and randomly stacked layered structure, (ii) an increased degree of Jahn–Teller distorted Mn3+ in the MnO6 octahedral sheets, (iii) effective stabilization of Mn3+, (iv) a high surface area, and (v) improved electrical conductivity. These results demonstrate that manganese oxides as structural and functional models of an oxygen-evolving complex (OEC) in photosystem II are promising catalysts for water oxidation in addition to Ni/Co-based oxides/hydroxides.

Iron porphyrins Fe-pE, Fe-mE, and Fe-oE were synthesized and their electrochemical behavior for CO reduction to CO has been investigated. The controlled potential electrolysis of Fe-mE gave exclusive 65% Faradaic efficiency (FE) whereas Fe-oE achieved quasi-quantitative 98% FE (2% H) for CO production.

In order to understand the effects of meso-substituents of the zinc porphyrins on optical, electrochemical, and photovoltaic properties, a series of porphyrins with different combinations of thienyl (S) and p-carboxyphenyl (A) groups as the meso substituents have been systematically synthesized and studied. The properties of zinc complexes 3S1A, trans-2S2A, cis-2S2A, and 1S3A were fully investigated by absorption and emission spectra, attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectra, density functional theory (DFT) calculations, electrochemical, photophysical, and photovoltaic measurements. With the increasing number of meso-thienyl groups, slight red-shifts of Soret and Q bands were observed in both absorption and emission spectra. All of the absorption spectra of zinc porphyrins on TiO 2 film show broadening and splitting of Soret bands because of excitonic coupling of porphyrins. ATR-FTIR spectra revealed likely modes to determine either a single arm (in 3S1A and trans-2S2A) or double arms (in 1S3A and cis-2S2A) attached on TiO 2 . Two factors of p-carboxyphenyl and thienyl groups affecting the devices performanceheavy atom effect and the amount of dye loading on TiO 2 are concluded. Overall, the power conversion efficiencies (η) of the devices exhibit the following order: 1S3A (3.0%) > cis-2S2A (2.5%) > trans-2S2A (1.8%) ≫ 3S1A (0.2%).

Inert aryl methyl ethers as coupling components via C–O activation have been established with a Ni catalyst for C–H activation of heteroarene. The key to simultaneous C–H/C–O bond activation is the use of sterically demanding o-tolylMgBr. The protocol is effective for a wide scope of substrates including naphthyl methyl ethers, anisoles, and a variety of other heteroarene derivatives. Detailed mechanistic studies indicated that the C–O cleavage is assisted via synergistic effect of nickel and Grignard reagent in this C–H/C–O reaction, which is supported by DFT calculation. At this stage, single-electron transfer can be ruled out as a main operative process for this tandem strategy.

Molecular catalysts possess numerous advantages over conventional heterogeneous catalysts in precise structure regulation, indepth mechanism understanding, and efficient metal utilization. Various molecular catalysts have been reported that efficiently catalyze reactions involved in artificial photosynthesis, however, these catalysts have been rarely considered in view of practical applications. With this review, firstly we demonstrate in the introduction that molecular catalysts can bring new opportunities to proton exchange membrane (PEM) electrolyzers. In the following parts, we provide an overview of molecular catalyst modified carbon materials developed for electrochemical water oxidation, proton reduction, and CO 2 reduction reactions. These materials and the involved immobilization strategies as well as characterization techniques may be directly employed in the investigations of application of molecular catalysts in PEM electrolyzers. The future scientific perspectives and challenges to advance this promising, yet underdeveloped technology for solar fuel production, integrating PEM electrolyzer with molecular-level catalysis, are discussed in the conclusions.

A series of porphyrin sensitizers that featured two electron-donating groups and dual anchoring groups that were connected through a porphine π-bridging unit have been synthesized and successfully applied in dye-sensitized solar cells (DSSCs). The presence of electron-donating groups had a significant influence on their spectroscopic, electrochemical, and photovoltaic properties. Overall, the dual anchoring groups gave tunable electronic properties and stronger attachment to TiO2 . These new dyes were readily synthesized in a minimum number of steps in gram-scale quantities. Optical and electrochemical data confirmed the advantages of these dyes for use as sensitizers in DSSCs. Porphyrins with electron-donating amino moieties provided improved charge separation and better charge-injection efficiencies for the studied dual-push-pull dyes. Attenuated total reflectance-Fourier-transform infrared (ATR-FTIR) and X-ray photoelectron spectroscopy of the porphyrin dyes on TiO2 suggest that both p-carboxyphenyl groups are attached onto TiO2, thereby resulting in strong attachment. Among these dyes, cis-Zn2BC2A, with two electron-donating 3,6-ditertbutyl-phenyl-carbazole groups and dual-anchoring p-carboxyphenyl groups, showed the highest efficiency of 4.07 %, with J(SC)=9.81 mA cm(-2), V(OC)=0.63 V, and FF=66 %. Our results also indicated a better photostability of the studied dual-anchored sensitizers compared to their mono-anchored analogues under identical conditions. These results provide insight into the developments of a new generation of high-efficiency and thermally stable porphyrin sensitizers.