Green hydrogen production from water is one attractive route to non-fossil fuel and a potential source of clean energy. Hydrogen is not only a zero-carbon energy source but can also be utilized as an efficient storage of electrical energy generated through various other sources, such as wind and solar. Cost-effective and environmentally benign direct hydrogen production through neutral water (∼pH 7) reduction is particularly challenging due to the low concentration of protons. There is currently a major need for easy-to-prepare, robust, as well as active electrode materials. Herein we report three new molecular electrodes that were prepared by anchoring commercially available, and environmentally benign cobalt-containing electrocatalysts with three different ligand frameworks (porphyrin, phthalocyanine, and corrin) on a structurally modified graphite foil surface. Under the studied reaction conditions (over 7 h at 22°C), the electrode with Co-porphyrin is the most efficient for the water reduction with starting ∼740 mV onset potential (OP) (vs. RHE, current density 2.5 mA/cm2) and a Tafel slope (TS) of 103 mV/dec. It is followed by the molecular electrodes having Co-phthalocyanine [825 mV (OP), 138 mV/dec (TS)] and Vitamin-B12 (Co-corrin moiety) [830 mV (OP), 194 mv/dec (TS)]. A clear time-dependent improvement (>200 mV over 3 h) in the H2 production overpotential with the Co-porphyrin-containing cathode was observed. This is attributed to the activation due to water coordination to the Co-center. A long-term chronopotentiometric stability test shows a steady production of hydrogen from all three cathode surfaces throughout seven hours, confirmed using an H2 needle sensor. At a current density of 10 mA/cm2, the Co-porphyrin-containing electrode showed a TOF value of 0.45 s−1 at 870 mV vs. RHE, whereas the Co-phthalocyanine and Vitamin-B12-containing electrodes showed 0.37 and 0.4 s−1 at 1.22 V and 1.15 V (vs. RHE), respectively.

Branched perfluorooctane sulfonic acid (PFOS) is recognized as a threatening environmental pollutant due to its high persistence and bioaccumulation in various environmental matrices as well as for its toxic effects on humans and wildlife even at very low concentrations. This study reports the first investigation of branched PFOS defluorination catalyzed by metal phthalocyanines. The reaction conditions were optimized using different reductants and temperatures. CobaltII phthalocyanine, when combined with TiIII citrate as a reducing agent, was able to defluorinate 10.9% of technical PFOS within 8 hours. In contrast, vitamin B12 only showed 2.4% defluorination during the same time period, under similar conditions. The defluorination mediated by the cobaltII phthalocyanine and TiIII citrate system corresponds to 54.5% of all branched PFOS isomers (br-PFOS isomers). Isomer-specific degradation was also investigated via high-resolution LC-orbitrap followed by their relative rates. The difference in catalytic efficacy of various phthalocyanine complexes is rationalized by their structures and electrochemical response. Lastly, a new defluorination mechanism is proposed based on the newly detected degradation products after the phthalocyanine treatment and previous studies. CobaltII phthalocyanine in the presence of TiIII citrate acts as an efficient reducing agent which was able to defluorinate 54.5% of all branched PFOS isomers.

Nano zero-valent metals (nZVMs) have been extensively utilized for decades in the reductive remediation of groundwater contaminated with chlorinated organic compounds, owing to their robust reducing capabilities, simple application, and cost-effectiveness. Nevertheless, there remains a dearth of information regarding the efficient reductive defluorination of linear or branched per- and polyfluoroalkyl substances (PFASs) using nZVMs as reductants, largely due to the absence of appropriate catalysts. In this work, various soluble porphyrin ligands [[meso‑tetra(4-carboxyphenyl)porphyrinato]cobalt(III)]Cl·7H2O (CoTCPP), [[meso‑tetra(4-sulfonatophenyl) porphyrinato]cobalt(III)]·9H2O (CoTPPS), and [[meso‑tetra(4-N-methylpyridyl) porphyrinato]cobalt(II)](I)4·4H2O (CoTMpyP) have been explored for defluorination of PFASs in the presence of the nZn0 as reductant. Among these, the cationic CoTMpyP showed best defluorination efficiencies for br-perfluorooctane sulfonate (PFOS) (94%), br-perfluorooctanoic acid (PFOA) (89%), and 3,7-Perfluorodecanoic acid (PFDA) (60%) after 1 day at 70 °C. The defluorination rate constant of this system (CoTMpyP-nZn0) is 88–164 times higher than the VB12-nZn0 system for the investigated br-PFASs. The CoTMpyP-nZn0 also performed effectively at room temperature (55% for br-PFOS, 55% for br-PFOA and 25% for 3,7-PFDA after 1day), demonstrating the great potential of in-situ application. The effect of various solubilizing substituents, electron transfer flow and corresponding PFASs defluorination pathways in the CoTMpyP-nZn0 system were investigated by both experiments and density functional theory (DFT) calculations. SYNOPSIS: Due to the unavailability of active catalysts, available information on reductive remediation of PFAS by zero-valent metals (ZVMs) is still inadequate. This study explores the effective defluorination of various branched PFASs using soluble porphyrin-ZVM systems and offers a systematic approach for designing the next generation of catalysts for PFAS remediation.

The instability of molecular electrodes under oxidative/reductive conditions and insufficient understanding of the metal oxide-based systems have slowed down the progress of H₂-based fuels. Efficient regeneration of the electrode's performance after prolonged use is another bottleneck of this research. This work represents the first example of a bifunctional and electrochemically regenerable molecular electrode which can be used for the unperturbed production of H₂ from water. Pyridyl linkers with flexible arms (–CH₂–CH₂–) on modified fluorine-doped carbon cloth (FCC) were used to anchor a highly active ruthenium electrocatalyst [Ru^II(mcbp)(H₂O)₂] (1) [mcbp²⁻ = 2,6-bis(1-methyl-4-(carboxylate)benzimidazol-2-yl)pyridine]. The pyridine unit of the linker replaces one of the water molecules of 1, which resulted in RuPFCC (ruthenium electrocatalyst anchored on –CH₂–CH₂–pyridine modified FCC), a high-performing electrode for oxygen evolution reaction [OER, overpotential of ∼215 mV] as well as hydrogen evolution reaction (HER, overpotential of ∼330 mV) at pH 7. A current density of ∼8 mA cm⁻² at 2.06 V (vs. RHE) and ∼−6 mA cm⁻² at −0.84 V (vs. RHE) with only 0.04 wt% loading of ruthenium was obtained. OER turnover of >7.4 × 10³ at 1.81 V in 48 h and HER turnover of >3.6 × 10³ at −0.79 V in 3 h were calculated. The activity of the OER anode after 48 h use could be electrochemically regenerated to ∼98% of its original activity while it serves as a HE cathode (evolving hydrogen) for 8 h. This electrode design can also be used for developing ultra-stable molecular electrodes with exciting electrochemical regeneration features, for other proton-dependent electrochemical processes.

The presence of per-and poly-fluoroalkyl substances (PFASs) in water is of global concern due to their high stability and toxicity even at very low concentrations. There are several technologies for the remediation of PFASs, but most of them are inadequate either due to limited effectiveness, high cost, or production of a large amount of sludge. Electrochemical oxidation (EO) technology shows great potential for large-scale application in the degradation of PFASs due to its simple procedure, low loading of chemicals, and least amount of waste. Here, we have reviewed the recent progress in EO methods for PFAS degradation, focusing on the last 10 years, to explore an efficient, cost-effective, and environmentally benign remediation technology. The effects of important parameters (e.g., anode material, current density, solution pH, electrolyte, plate distance, and electrical connector type) are summarized and evaluated. Also, the energy consumption, the consequence of different PFASs functional groups, and water matrices are discussed to provide an insight that is pivotal for developing new EO materials and technologies. The proposed degradation pathways of shorter-chain PFAS by-products during EO of PFAS are also discussed.

The low stability of the electrocatalysts at water oxidation (WO) conditions and the use of expensive noble metals have obstructed large-scale H₂ production from water. Herein, we report the electrocatalytic WO activity of a cobalt-containing, water-soluble molecular WO electrocatalyst [Co^II(mcbp)(OH₂)] (1) [mcbp²⁻=2,6-bis(1-methyl-4-(carboxylate)benzimidazol-2-yl)pyridine] in homogeneous conditions (overpotential of 510 mV at pH 7 phosphate buffer) and after anchoring it on pyridine-modified fluorine-doped carbon cloth (PFCC). The formation of cobalt phosphate was identified only after 4 h continuous oxygen evolution in homogeneous conditions. Interestingly, a significant enhancement of the stability and WO activity (current density of 5.4 mA/cm² at 1.75 V) was observed for 1 after anchoring onto PFCC, resulting in a turnover (TO) of >3.6×10³ and average TOF of 0.05 s⁻¹ at 1.55 V (pH 7) over 20 h. A total TO of >21×10³ over 8 days was calculated. The electrode allowed regeneration of∼ 85 % of the WO activity electrochemically after 36 h of continuous oxygen evolution.

Vitamin B₁₂ (VB₁₂) has been reported to degrade PFOS in the presence of Ti^III citrate at 70 °C. Porphyrin-based catalysts have emerged as VB₁₂ analogues and have been successfully used in various fields of research due to their interesting structural and electronic properties. However, there is inadequate information on the use of these porphyrin-based metal complexes in the defluorination of PFOS. We have therefore explored a series of porphyrin-based metal complexes for the degradation of PFOS. Co^II–5,10,15,20-tetraphenyl-21H,23H-porphyrin (Co^II–TPP), Co^II–5,10,15,20-tetrakis(4-methoxyphenyl)-21H,23H-porphyrin (Co^II–M-TPP), and Co^III–M-TPP exhibited efficient reductive defluorination of the branched PFOS. Within 5–8 h, these compounds achieved the same level of PFOS defluorination as VB₁₂ achieved in 7–10 days. For branched isomers, the specific removal rate of the Co^II–TPP–Ti^III citrate system is 64–105 times higher than that for VB₁₂–Ti^III citrate. Moreover, the Co^II–TPP–Ti^III citrate system displayed efficient (51%) defluorination for the branched PFOS (br-PFOS) in 1 day even at room temperature (25 °C). The effects of the iron and cobalt metal centers, reaction pH, and several reductants (NaBH₄, nanosized zerovalent zinc (nZn⁰), and Ti^III citrate) were systematically investigated. Based on the analysis of the products and previously published reports, a new possible defluorination pathway of branched PFOS is also proposed. 

Electrochemical water splitting constitutes one of the most promising strategies for converting water into hydrogen-based fuels, and this technology is predicted to play a key role in the transition towards a carbon-neutral energy economy. To enable the design of cost-effective electrolysis cells based on this technology, new and more efficient anodes with augmented water splitting activity and stability will be required. Herein, we report an active molecular Ru-based catalyst for electrochemically-driven water oxidation (overpotential of ∼395 mV at pH 7 phosphate buffer) and two simple methods for preparing anodes by attaching this catalyst onto glassy carbon through multi-walled carbon nanotubes to improve stability as well as reactivity. The anodes modified with the molecular catalyst were characterized by a broad toolbox of microscopy and spectroscopy techniques, and interestingly no RuO2 formation was detected during electrocatalysis over 4 h. These results demonstrate that the herein presented strategy can be used to prepare anodes that rival the performance of state-of-the-art metal oxide anodes.

Ceric(IV) ammonium nitrate (CAN) in aqueous medium acts as an excellent precipitating agent for perfluorooctanesulfonic acid (PFOS). The Ce(IV) center plays a crucial role. Interestingly, Ce(III) chloride showed much less effectiveness under similar conditions. The efficacy of CAN was reduced upon changing the substrate to perfluorooctanoic acid (PFOA).

Fossil fuel shortage and severe climate changes due to global warming have prompted extensive research on carbon-neutral and renewable energy resources. Hydrogen gas (H-2), a clean and high energy density fuel, has emerged as a potential solution for both fulfilling energy demands and diminishing the emission of greenhouse gases. Currently, water oxidation (WO) constitutes the bottleneck in the overall process of producing H-2 from water. As a result, the design of efficient catalysts for WO has become an intensively pursued area of research in recent years. Among all the molecular catalysts reported to date, ruthenium-based catalysts have attracted particular attention due to their robust nature and higher activity compared to catalysts based on other transition metals. Over the past two decades, we and others have studied a wide range of ruthenium complexes displaying impressive catalytic performance for WO in terms of turnover number (TON) and turnover frequency (TOF). However, to produce practically applicable electrochemical, photochemical, or photo-electrochemical WO reactors, further improvement of the catalysts' structure to decrease the overpotential and increase the WO rate is of utmost importance. WO reaction, that is, the production of molecular oxygen and protons from water, requires the formation of an O-O bond through the orchestration of multiple proton and electron transfers. Promotion of these processes using redox noninnocent ligand frameworks that can accept and transfer electrons has therefore attracted substantial attention. The strategic modifications of the ligand structure in ruthenium complexes to enable proton-coupled electron transfer (PCET) and atom proton transfer (APT; in the context of WO, it is the oxygen atom (metal oxo) transfer to the oxygen atom of a water molecule in concert with proton transfer to another water molecule) to facilitate the O-O bond formation have played a central role in these efforts. In particular, promising results have been obtained with ligand frameworks containing carboxylic acid groups that either are directly bonded to the metal center or reside in the close vicinity. The improvement of redox and chemical properties of the catalysts by introduction of carboxylate groups in the ligands has proven to be quite general as demonstrated for a range of mono- and dinudear ruthenium complexes featuring ligand scaffolds based on pyridine, imidazole, and pyridazine cores. In the first coordination sphere, the carboxylate groups are firmly coordinated to the metal center as negatively charged ligands, improving the stability of the complexes and preventing metal leaching during catalysis. Another important phenomenon is the reduction of the potentials required for the formation of higher valent intermediates, especially metal-oxo species, which take active part in the key O-O bond formation step. Furthermore, the free carboxylic acid/carboxylate units in the proximity to the active center have shown exciting proton donor/acceptor properties (through PCET or APT, chemically noninnocent) that can dramatically improve the rate as well as the overpotential of the WO reaction.