One clean alternative to fossil fuels would be to split water using sunlight. However, to achieve this goal, researchers still need to fully understand and control several key chemical reactions. One ...of them is the catalytic oxidation of water to molecular oxygen, which also occurs at the oxygen evolving center of photosystem II in green plants and algae. Despite its importance for biology and renewable energy, the mechanism of this reaction is not fully understood. Transition metal water oxidation catalysts in homogeneous media offer a superb platform for researchers to investigate and extract the crucial information to describe the different steps involved in this complex reaction accurately. The mechanistic information extracted at a molecular level allows researchers to understand both the factors that govern this reaction and the ones that derail the system to cause decomposition. As a result, rugged and efficient water oxidation catalysts with potential technological applications can be developed. In this Account, we discuss the current mechanistic understanding of the water oxidation reaction catalyzed by transition metals in the homogeneous phase, based on work developed in our laboratories and complemented by research from other groups. Rather than reviewing all of the catalysts described to date, we focus systematically on the several key elements and their rationale from molecules studied in homogeneous media. We organize these catalysts based on how the crucial oxygen–oxygen bond step takes place, whether via a water nucleophilic attack or via the interaction of two M–O units, rather than based on the nuclearity of the water oxidation catalysts. Furthermore we have used DFT methodology to characterize key intermediates and transition states. The combination of both theory and experiments has allowed us to get a complete view of the water oxidation cycle for the different catalysts studied. Finally, we also describe the various deactivation pathways for these catalysts.
Covalent organic frameworks (COFs) are crystalline porous organic polymers built from covalent organic blocks that can be photochemically active when incorporating organic semiconducting units, such ...as triazine rings or diacetylene bridges. The bandgap, charge separation capacity, porosity, wettability, and chemical stability of COFs can be tuned by properly choosing their constitutive building blocks, by extension of conjugation, by adjustment of the size and crystallinity of the pores, and by synthetic post-functionalization. This review focuses on the recent uses of COFs as photoactive platforms for the hydrogen evolution reaction (HER), in which usually metal nanoparticles (NPs) or metallic compounds (generally Pt-based) act as co-catalysts. The most promising COF-based photocatalytic HER systems will be discussed, and special emphasis will be placed on rationalizing their structure and light-harvesting properties in relation to their catalytic activity and stability under turnover conditions. Finally, the aspects that need to be improved in the coming years will be discussed, such as the degree of dispersibility in water, the global photocatalytic efficiency, and the robustness and stability of the hybrid systems, putting emphasis on both the COF and the metal co-catalyst.
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•Conversion of H2O into H2 and O2 by sunlight could be a solution for energy shortage.•Water oxidation (WO) is mechanistically complex and thermodynamically uphill.•During the last ...five years a wide range of WO catalysts have been reported.•Main advances in chemical, electrochemical and photochemical WO are described.•The best examples of photo-electrochemical cells are also included.
Hydrogen release from the splitting of water by simply using sunlight as the only energy source is an old human dream that could finally become a reality. This process involves both the reduction and oxidation of water into hydrogen and oxygen, respectively. While the first process has been fairly overcome, the conversion of water into oxygen has been traditionally the bottleneck process hampering the development of a sustainable hydrogen production based on water splitting. Fortunately, a revolution in this field has occurred during the past decade, since many research groups have been conducting an intense research in this area.
Thus, while molecular, well-characterized catalysts able to oxidize water were scarce just five years ago, now a wide range of transition metal based compounds has been reported as active catalysts for this transformation. This review reports the most prominent key advances in the field, covering either examples where the catalysis is triggered chemically, electrochemically or photochemically.
Metallothioneins (MTs) are a superfamily of Cys-rich, low-molecular weight metalloproteins that bind heavy metal ions. These cytosolic metallopeptides, which exist in most living organisms, are ...thought to be involved in metal homeostasis, metal detoxification, and oxidative stress protection. In this work, we characterise the Zn(II)- and Cd(II)-binding abilities of plant type 3 and type 4 MTs identified in soybean and sunflower, both of them being His-containing peptides. The recombinant metal-MT complexes synthesised in Zn(II) or Cd(II)-enriched
Escherichia coli
cultures have been analysed by ESI-MS, and CD, ICP-AES, and UV spectroscopies. His-to-Ala type 3 MT mutants have also been constructed and synthesised for the study of the role of His in divalent metal ion coordination. The results show comparable divalent metal-binding capacities for the MTs of type 3, and suggest, for the first time, the participation of their conserved C-term His residues in metal binding. Interesting features for the Zn(II)-binding abilities of type 4 MTs are also reported, as their variable His content may be considered crucial for their biological performance.
Metallothioneins are small Cys-rich peptides capable of coordinating metal ions, and proposed to be involved in radical stress. The four Zn(ii)-GmMT complexes of soybean (Glycine max) were ...recombinantly synthesised and exposed to oxidative (HO˙) and reductive (H˙ atoms and eaq-) stress conditions. Gamma-irradiation was used to simulate the endogenous formation of the reactive species in both aqueous solutions and unsaturated lipid vesicle suspensions, a biomimetic model that showed that tandem protein/lipid damage occurs, in particular under reductive radical stress. This is due to the formation of diffusible sulphur-centred radicals, which migrate from the aqueous phase to the lipid bilayer and are thus able to transform the cis double bond of the oleate moiety into the trans isomer. Among the amino acid residues present in GmMTs, Cys is one of the most sensitive residues towards the attack of free radicals, thus suggesting metal-clusters to be good interceptors of free radicals. Also Met, Tyr and Phe residues are sensitive amino acid sites of attack under both oxidative and reductive conditions. The modification of the Zn(ii)-GmMT complexes, in particular isoform 2, was monitored by Raman spectroscopy and mass spectrometry. Free radical stress on the Zn(ii)-GmMT complexes is able to induce significant structural changes such as partial deconstruction and/or rearrangement of the metal clusters, but not the complete demetallation of the proteins nor breaking of the backbone, thus confirming their capability to act as protectors under free radical stress conditions.
Both global warming and limited fossil resources make the transition from fossil to solar fuels an urgent matter. In this regard, the splitting of water activated by sunlight is a sustainable and ...carbon‐free new energy conversion scheme able to produce efficient technological devices. The availability of appropriate catalysts is essential for the proper kinetics of the two key processes involved, namely, the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER). During the last decade, ruthenium nanoparticle derivatives have emerged as true potential substitutes for the state‐of‐the‐art platinum and iridium oxide species for the HER and OER, respectively. Thus, after a summary of the most common methods for catalyst benchmarking, this review covers the most significant developments of ruthenium‐based nanoparticles used as catalysts for the water‐splitting process. Furthermore, the key factors that govern the catalytic performance of these nanocatalysts are discussed in view of future research directions.
Breaking it down: Catalysts for the hydrogen and oxygen evolution reactions are key components of new sustainable energy conversion schemes based on water splitting and sunlight. This review covers the most significant developments in ruthenium‐based nanoparticles as catalysts for these processes, focusing on factors that govern their performance.
Metallothioneins (MTs) constitute a superfamily of ubiquitous metal-binding proteins of low molecular weight and high Cys content. They are involved in metal homeostasis and detoxification, amongst ...other proposed biological functions. Two MT isoforms (SpMTA and SpMTB) have been reported in the echinoderm Strongylocentrotus purpuratus (sea urchin), both containing 20 Cys residues and presenting extremely similar sequences, although showing distinct tissular and ontogenic expression patterns. Although exhaustive information is available for the Cd(II)-SpMTA complex, this including the full resolution of its 3D structure, no data has been reported concerning either SpMTA Zn(II) and Cu(I) binding properties, or the characterization of SpMTB at protein level. In this work, both the SpMTA and SpMTB isoforms, as well as their separate α and β domains, have been recombinantly synthesized in the presence of Zn(II), Cd(II) or Cu(II), and the corresponding metal complexes have been analyzed using electrospray mass spectrometry, and CD, ICP-AES and UV–vis spectroscopies. The results clearly show a better performance of isoform A when binding Zn(II) and Cd(II), and of isoform B when coordinating Cu(I). Thus, our results confirm the differential metal binding preference of SpMTA and SpMTB, which, together with the reported induction pattern of the respective genes, highlights how also in Echinodermata the MT polymorphism may be linked to the evolution of different physiological roles.
▸ SpMTA shows a better performance when binding Zn(II) and Cd(II). ▸ SpMTB shows a better performance when binding Cu(I). ▸ The β domain is responsible for the lower divalent metal binding capacity of SpMTB. ▸ The α and β domains contribute to the enhanced capacity of SpMTB for Cu(I) binding.
Water oxidation to dioxygen is one of the key reactions that need to be mastered for the design of practical devices based on water splitting with sunlight. In this context, water oxidation catalysts ...based on first‐row transition metal complexes are highly desirable due to their low cost and their synthetic versatility and tunability through rational ligand design. A new family of dianionic bpy‐amidate ligands of general formula H2LNn− (LN is 2,2′‐bipyridine‐6,6′‐dicarboxamide) substituted with phenyl or naphthyl redox non‐innocent moieties is described. A detailed electrochemical analysis of (L4)Cu2− (L4=4,4′‐((2,2′‐bipyridine‐6,6′‐dicarbonyl)bis(azanediyl))dibenzenesulfonate) at pH 11.6 shows the presence of a large electrocatalytic wave for water oxidation catalysis at an η=830 mV. Combined experimental and computational evidence, support an all ligand‐based process with redox events taking place at the aryl‐amide groups and at the hydroxido ligands.
A family of Cu‐based complexes bearing dianionic bpy‐amidate ligands have been prepared and characterized by spectroscopic and electrochemical techniques. The new complexes are capable of performing water oxidation catalysis at overpotentials between 557–830 mV pH 11.6. A detailed electrocatalytic study in combination with computational calculations revealed the all ligand‐based nature of the electron transfer processes involved in the catalytic cycle.
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