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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/cm 2 ) 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-B 12 (Co-corrin moiety) [830 mV (OP), 194 mv/dec (TS)]. A clear time-dependent improvement (>200 mV over 3 h) in the H 2 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 H 2 needle sensor. At a current density of 10 mA/cm 2 , 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-B 12 -containing electrodes showed 0.37 and 0.4 s -1 at 1.22 V and 1.15 V (vs. RHE), respectively., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2024 Toledo-Carrillo, García-Rodríguez, Morallón, Cazorla-Amorós, Ye, Kundi, Kumar, Verho, Dutta, Åkermark and Das.)

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·7H 2 O (CoTCPP), [[meso‑tetra(4-sulfonatophenyl) porphyrinato]cobalt(III)]·9H 2 O (CoTPPS), and [[meso‑tetra(4-N-methylpyridyl) porphyrinato]cobalt(II)](I) 4 ·4H 2 O (CoTMpyP) have been explored for defluorination of PFASs in the presence of the nZn 0 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-nZn 0 ) is 88-164 times higher than the VB 12 -nZn 0 system for the investigated br-PFASs. The CoTMpyP-nZn 0 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-nZn 0 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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

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., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:Prof. Naresh Kumar reports financial support was provided by Australian Research Council. Prof. Naresh Kumar reports a relationship with University of New South Wales that includes: employment., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Vitamin B 12 (VB 12 ) has been reported to degrade PFOS in the presence of Ti III citrate at 70 °C. Porphyrin-based catalysts have emerged as VB 12 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-21 H ,23 H -porphyrin (Co II -TPP), Co II -5,10,15,20-tetrakis(4-methoxyphenyl)-21 H ,23 H -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 VB 12 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 VB 12 -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 (NaBH 4 , nanosized zerovalent zinc (nZn 0 ), 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 RuO 2 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.

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 dinuclear 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.

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)., Competing Interests: Authors declare no conflict of interests., (This journal is © The Royal Society of Chemistry.)

The highly active ruthenium-based water oxidation catalyst [Ru X (mcbp)(OH n )(py) 2 ] [mcbp 2- =2,6-bis(1-methyl-4-(carboxylate)benzimidazol-2-yl)pyridine; n=2, 1, and 0 for X=II, III, and IV, respectively], can be generated in a mixture of Ru III and Ru IV states from either [Ru II (mcbp)(py) 2 ] or [Ru III (Hmcbp)(py) 2 ] 2+ precursors. The precursor complexes are isolated and characterized by single-crystal X-ray analysis, NMR, UV/Vis, EPR, and FTIR spectroscopy, ESI-HRMS, and elemental analysis, and their redox properties are studied in detail by electrochemical and spectroscopic methods. Unlike the parent catalyst [Ru(tda) (py) 2 ] (tda 2- =[2,2':6',2''-terpyridine]-6,6''-dicarboxylate), for which full transformation into the catalytically active species [Ru IV (tda)(O)(py) 2 ] could not be carried out, stoichiometric generation of the catalytically active Ru-aqua complex [Ru X (mcbp)(OH n )(py) 2 ] from the Ru II precursor was achieved under mild conditions (pH 7.0) and short reaction times. The redox properties of the catalyst were studied and its activity for electrocatalytic water oxidation was evaluated, reaching a maximum turnover frequency (TOF max ) of around 40 000 s -1 at pH 9.0 (from foot-of-the-wave analysis), which is comparable to the activity of the state-of-the-art catalyst [Ru IV (tda)(O)(py) 2 ]., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Catalysts for oxidation of water to molecular oxygen are essential in solar-driven water splitting. In order to develop more efficient catalysts for this oxidatively demanding reaction, it is vital to have mechanistic insight in order to understand how the catalysts operate. Herein, we report the mechanistic details associated with the two Ru catalysts 1 and 2. Insight into the mechanistic landscape of water oxidation catalyzed by the two single-site Ru catalysts was revealed by the use of a combination of experimental techniques and quantum chemical calculations. On the basis of the obtained results, detailed mechanisms for oxidation of water by complexes 1 and 2 are proposed. Although the two complexes are structurally related, two deviating mechanistic scenarios are proposed with metal-ligand cooperation being an important feature in both processes. The proposed mechanistic platforms provide insight for the activation of water or related small molecules through nontraditional and previously unexplored routes.

Photocatalytic water oxidation represents a key process in conversion of solar energy into fuels and can be facilitated by the use of molecular transition metal-based catalysts. A novel straightforward approach for covalent linking of the catalytic units to other moieties is demonstrated by preparation of a dinuclear complex containing two [Ru(pdc)(pic) 3 ]-derived units (pdc = 2,6-pyridinedicarboxylate, pic = 4-picoline). The activity of this complex towards chemical and photochemical oxidation of water was evaluated and a detailed insight is given into the interactions between the catalyst and acetonitrile, a common co-solvent employed to increase solubility of water oxidation catalysts. The solvent-induced transformations were studied by electrochemical and spectroscopic techniques and the relevant quantitative parameters were extracted.

Water oxidation is a fundamental step in artificial photosynthesis for solar fuels production. In this study, we report a single-site Ru-based water oxidation catalyst, housing a dicarboxylate-benzimidazole ligand, that mediates both chemical and light-driven oxidation of water efficiently under neutral conditions. The importance of the incorporation of the negatively charged ligand framework is manifested in the low redox potentials of the developed complex, which allows water oxidation to be driven by the mild one-electron oxidant [Ru(bpy) 3 ] 3+ (bpy=2,2'-bipyridine). Furthermore, combined experimental and DFT studies provide insight into the mechanistic details of the catalytic cycle., (© 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Catalysts for the oxidation of H2O are an integral component of solar energy to fuel conversion technologies. Although catalysts based on scarce and precious metals have been recognized as efficient catalysts for H2O oxidation, catalysts composed of inexpensive and earth-abundant element(s) are essential for realizing economically viable energy conversion technologies. This Perspective summarizes recent advances in the field of designing homogeneous water oxidation catalysts (WOCs) based on Mn, Fe, Co and Cu. It reviews the state of the art catalysts, provides insight into their catalytic mechanisms and discusses future challenges in designing bioinspired catalysts based on earth-abundant metals for the oxidation of H2O.

The synthesis of two molecular iron complexes, a dinuclear iron(iii,iii) complex and a nonanuclear iron complex, based on the dinucleating ligand 2,2'-(2-hydroxy-5-methyl-1,3-phenylene)bis(1H-benzo[d]imidazole-4-carboxylic acid) is described. The two iron complexes were found to drive the oxidation of water by the one-electron oxidant [Ru(bpy)3](3+).

Artificial photosynthesis represents an attractive way of converting solar energy into storable chemical energy. The H2O oxidation half-reaction, which is essential for producing the necessary reduction equivalents, is an energy-demanding transformation associated with a high kinetic barrier. Herein we present a couple of efficient Ru-based catalysts capable of mediating this four-proton-four-electron oxidation. We have focused on the incorporation of negatively charged ligands, such as carboxylate, phenol, and imidazole, into the catalysts to decrease the redox potentials. This account describes our work in designing Ru catalysts based on this idea. The presence of the negatively charged ligands is crucial for stabilizing the metal centers, allowing for light-driven H2O oxidation. Mechanistic details associated with the designed catalysts are also presented., (© 2016 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Herein is presented a single-site Ru complex bearing a carboxamide-based ligand that efficiently manages to carry out the four-electron oxidation of H2O. The incorporation of the negatively charged ligand framework significantly lowered the redox potentials of the Ru complex, allowing H2O oxidation to be driven by the mild oxidant [Ru(bpy)3](3+). This work highlights that the inclusion of amide moieties into metal complexes thus offers access to highly active H2O oxidation catalysts.

Insight into how H2 O is oxidized to O2 is envisioned to facilitate the rational design of artificial water oxidation catalysts, which is a vital component in solar-to-fuel conversion schemes. Herein, we report on the mechanistic features associated with a dinuclear Ru-based water oxidation catalyst. The catalytic action of the designed Ru complex was studied by the combined use of high-resolution mass spectrometry, electrochemistry, and quantum chemical calculations. Based on the obtained results, it is suggested that the designed ligand scaffold in Ru complex 1 has a non-innocent behavior, in which metal-ligand cooperation is an important part during the four-electron oxidation of H2 O. This feature is vital for the observed catalytic efficiency and highlights that the preparation of catalysts housing non-innocent molecular frameworks could be a general strategy for accessing efficient catalysts for activation of H2 O., (© 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of Creative Commons Attribution NonCommercial-NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.)

The increasing energy demand calls for the development of sustainable energy conversion processes. Here, the splitting of H2O to O2 and H2, or related fuels, constitutes an excellent example of solar-to-fuel conversion schemes. The critical component in such schemes has proven to be the catalyst responsible for mediating the four-electron oxidation of H2O to O2. Herein, we report on the unexpected formation of a single-site Ru complex from a ligand envisioned to accommodate two metal centers. Surprising N-N bond cleavage of the designed dinuclear ligand during metal complexation resulted in a single-site Ru complex carrying a carboxylate-amide motif. This ligand lowered the redox potential of the Ru complex sufficiently to permit H2O oxidation to be carried out by the mild one-electron oxidant [Ru(bpy)3](3+) (bpy = 2,2'-bipyridine). The work thus highlights that strongly electron-donating ligands are important elements in the design of novel, efficient H2O oxidation catalysts.

Herein, we describe the use of Pd nanoparticles immobilized on an amino-functionalized siliceous mesocellular foam for the catalytic oxidation of H2O. The Pd nanocatalyst proved to be capable of mediating the four-electron oxidation of H2O to O2, both chemically and photochemically. The Pd nanocatalyst is easy to prepare and shows high chemical stability, low leaching, and recyclability. Together with its promising catalytic activity, these features make the Pd nanocatalyst of potential interest for future sustainable solar-fuel production., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Herein is described the preparation of a dinuclear molecular Ru catalyst for H2O oxidation. The prepared catalyst mediates the photochemical oxidation of H2O with an efficiency comparable to state-of-the-art catalysts.

The synthesis of Mn-based catalysts to mimic the structural and catalytic properties of the oxygen-evolving complex in photosystem II is a long-standing goal for researchers. An interesting result in this field came with the synthesis of a Mn complex that enables water oxidation driven by the mild single-electron oxidant [Ru(bpy)3](3+). On the basis of hybrid density functional calculations, we herein propose a water oxidation mechanism for this bioinspired Mn catalyst, where the crucial O-O bond formation proceeds from the formal Mn4(IV,IV,IV,V) state by direct coupling of a Mn(IV)-bound terminal oxyl radical and a di-Mn bridging oxo group, a mechanism quite similar to the presently leading suggestion for the natural system. Of importance here is that the designed ligand is shown to be redox-active and can therefore store redox equivalents during the catalytic transitions, thereby alleviating the redox processes at the Mn centers.

During recent years significant progress has been made towards the realization of a sustainable and carbon-neutral energy economy. One promising approach is photochemical splitting of H2O into O2 and solar fuels, such as H2. However, the bottleneck in such artificial photosynthetic schemes is the H2O oxidation half reaction where more efficient catalysts are required that lower the kinetic barrier for this process. In particular catalysts based on earth-abundant metals are highly attractive compared to catalysts comprised of noble metals. We have now synthesized a library of dinuclear Mn2(II,III) catalysts for H2O oxidation and studied how the incorporation of different substituents affected the electronics and catalytic efficiency. It was found that the incorporation of a distal carboxyl group into the ligand scaffold resulted in a catalyst with increased catalytic activity, most likely because of the fact that the distal group is able to promote proton-coupled electron transfer (PCET) from the high-valent Mn species, thus facilitating O-O bond formation.

Two dinuclear and one mononuclear ruthenium complexes containing neutral polypyridyl ligands have been synthesised as pre-water oxidation catalysts and characterised by (1)H and (13)C NMR spectroscopy and ESI-MS. Their catalytic water oxidation properties in the presence of [Ce(NH(4))(2)(NO(3))(6)] (Ce(IV)) as oxidant at pH 1.0 have been investigated. At low concentrations of Ce(IV) (5 mM), high turnover numbers of up to 4500 have been achieved. An (18)O-labelling experiment established that both O atoms in the evolved O(2) originate from water. Combined electrochemical study and electrospray ionisation mass spectrometric analysis suggest that ligand exchange between coordinated 4-picoline and free water produces Ru aquo species as the real water oxidation catalysts., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The new Ru complex 8 containing the bio-inspired ligand 7 was successfully synthesized and characterized. Complex 8 efficiently catalyzes water oxidation using Ce(IV) and Ru(III) as chemical oxidants. More importantly, this complex has a sufficiently low overpotential to utilize ruthenium polypyridyl-type complexes as photosensitizers., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We have developed molecular mechanics parameters for Ru(II)-polypyridyl coordination compounds with the MM3 force field in MacroModel. X-ray structures, together with a B3LYP frequency calculation on a model system, have been utilized in the parametrization. The performance of the force field and the quality of each parameter is analyzed. A clear qualitative correlation have been found between coordination geometry and emission properties for the ruthenium polypyridyl complexes examined in this paper.

A series of Ru(II) compounds and salts have been synthesized: [Ru(6-carboxylato-bpy)(2)] (5), [Ru(6-carboxylato-bpy)(tpy)]PF(6) (9), [Ru(tpy)(2)](PF(6))(2) (8), and [Ru(bpy)(2)(Pic)]PF(6) (11), where 6-carboxy-bpy (1) = 6-carboxy-2,2'-bipyridine, tpy (2) = 2,2':6',2"-terpyridine, and Pic = 2-carboxylatopyridine. The compounds have been characterized by NMR, electrospray mass spectrometry (ESI-MS), cyclic voltammetry, absorption and emission spectroscopy (at 100, 140, and 298 K), and single-crystal X-ray diffraction (complex 5). Complex 5 crystallizes in the monoclinic system, space group P2(1)/n, formula RuC(22)H(14)N(4)O(4).C(2)H(5)OH, with a = 11.088(3) Å, b = 11.226(3) Å, c = 35.283(9) Å, beta = 91.41(2) degrees, and Z = 8. A linear dependence on the number of coordinated carboxylato groups and the electrochemical redox potentials was found, ca. 0.4 V lower reduction potential for the oxidation step (Ru(II/III)) per carboxylate group. Also, to the best of our knowledge, these are the first examples (9, 11) of mononuclear Ru(II) complexes containing a carboxypyridine-ruthenium moiety displaying any luminescence emission.