Rational Design of Improved Ru Containing Fe-Based Metal-Organic Framework (MOF) Photoanode for Artificial Photosynthesis.

Metal-Organic Frameworks (MOFs) recently emerged as a new platform for the realization of integrated devices for artificial photosynthesis. However, there remain few demonstrations of rational tuning of such devices for improved performance. Here, a fast molecular water oxidation catalyst working via water nucleophilic attack is integrated into the MOF MIL-142, wherein Fe3O nodes absorb visible light, leading to charge separation. Materials are characterized by a range of structural and spectroscopic techniques. New, [Ru(tpy)(Qc)(H2O)]+ (tpy = 2,2':6',2″-terpyridine and Qc = 8-quinolinecarboxylate)-doped Fe MIL-142 achieved a high photocurrent (1.6 × 10-3 A·cm-2) in photo-electrocatalytic water splitting at pH = 1. Unassisted photocatalytic H2 evolution is also reported with Pt as the co-catalyst (4.8 µmol g-1 min-1). The high activity of this new system enables hydrogen gas capture from an easy-to-manufacture, scaled-up prototype utilizing MOF deposited on FTO glass as a photoanode. These findings provide insights for the development of MOF-based light-driven water-splitting assemblies utilizing a minimal amount of precious metals and Fe-based photosensitizers.

Pentanuclear iron complex for water oxidation: spectroscopic analysis of reactive intermediates in solution and catalyst immobilization into the MOF-based photoanode.

Photoelectrochemical water splitting can produce green hydrogen for industrial use and CO2-neutral transportation, ensuring the transition from fossil fuels to green, renewable energy sources. The iron-based electrocatalyst [FeII4FeIII(µ-3-O)(µ-L)6]3+ (LH = 3,5-bis(2-pyridyl)pyrazole) (1), discovered in 2016, is one of the fastest molecular water oxidation catalysts (WOC) based on earth-abundant elements. However, its water oxidation reaction mechanism has not been yet fully elucidated. Here, we present in situ X-ray spectroscopy and electron paramagnetic resonance (EPR) analysis of electrochemical water oxidation reaction (WOR) promoted by (1) in water-acetonitrile solution. We observed transient reactive intermediates during the in situ electrochemical WOR, consistent with a coordination sphere expansion prior to the onset of catalytic current. At a pre-catalytic (~+1.1 V vs. Ag/AgCl) potential, the distinct g~2.0 EPR signal assigned to FeIII/FeIV interaction was observed. Prolonged bulk electrolysis at catalytic (~+1.6 V vs. Ag/AgCl) potential leads to the further oxidation of Fe centers in (1). At the steady state achieved with such electrolysis, the formation of hypervalent FeV=O and FeIV=O catalytic intermediates was inferred with XANES and EXAFS fitting, detecting a short Fe=O bond at ~1.6 Å. (1) was embedded into MIL-126 MOF with the formation of (1)-MIL-126 composite. The latter was tested in photoelectrochemical WOR and demonstrated an improvement of electrocatalytic current upon visible light irradiation in acidic (pH=2) water solution. The presented spectroscopic analysis gives further insight into the catalytic pathways of multinuclear systems and should help the subsequent development of more energy- and cost-effective catalysts of water splitting based on earth-abundant metals. Photoelectrocatalytic activity of (1)-MIL-126 confirms the possibility of creating an assembly of (1) inside a solid support and boosting it with solar irradiation towards industrial applications of the catalyst.

Revisit the E2 Domain of Amyloid Precursor Protein: Ferroxidase, Superoxide and Peroxynitrite Scavenging Activities.

Amyloid precursor protein (APP) is the biological precursor of ß-amyloids, a known histopathological hallmark associated with Alzheimer's disease (AD). The function of APP is of great interest yet remains elusive. One of the extracellular domains of APP, the E2 domain, has been proposed to possess ferroxidase activity and affect neuronal iron homeostasis. However, contradicting evidence has been reported, and its precise role remains inconclusive. Here, we studied the Cu-binding site of the E2 domain using extended X-ray absorption fine structure (EXAFS), UV-vis, and electron paramagnetic resonance (EPR) and discovered that a new labile water ligand coordinates to the Cu(II) cofactor in addition to the four known histidines. We explored the proposed ferroxidase activity of the Cu(II)-E2 domain through reactions with ferrous iron and observed single-turnover ferrous oxidation activity with a rate up to 1.0 × 102 M-1 s-1. Cu(I)-E2 reacted with molecular oxygen at a rate of only 5.3 M-1 s-1, which would restrict any potential multiturnover ferroxidase activity to this slow rate and prevents observation of activity under multiturnover conditions. The positive electrostatic potential surface of the protein indicates possible reactivity with negatively charged small substrates such as superoxide radicals (O2•-) and peroxynitrite (ONOO-) that are major contributors to the oxidative stress prevalent in the extracellular environment. Our assays showed that Cu(I)-E2 can remove O2•- at a rate of 1.6 × 105 M-1 s-1, which is slower than the rates of native SODs. However, the reaction between Cu(I)-E2 and ONOO- achieved a rate of 1.1 × 105 M-1 s-1, comparable to native ONOO- scavenger peroxiredoxins (105-107 M-1 s-1). Therefore, the E2 domain of APP can serve as an enzymatic site that may function as a ferroxidase under substrate-limiting conditions, a supplemental O2•- scavenger, and an ONOO- remover in the vicinity of the cellular iron efflux channel and protect neuron cells from reactive oxygen species (ROS) and reactive nitrogen species (RNS) damage.

Systematic Influence of Electronic Modification of Ligands on the Catalytic Rate of Water Oxidation by a Single-Site Ru-Based Catalyst.

Catalytic water oxidation is an important process for the development of clean energy solutions and energy storage. Despite the significant number of reports on active catalysts, systematic control of the catalytic activity remains elusive. In this study, descriptors are explored that can be correlated with catalytic activity. [Ru(tpy)(pic)2 (H2 O)](NO3 )2 and [Ru(EtO-tpy)(pic)2 (H2 O)](NO3 )2 (where tpy=2,2' : 6',2"-terpyridine, EtO-tpy=4'-(ethoxy)-2,2':6',2"-terpyridine, pic=4-picoline) are synthesized and characterized by NMR, UV/Vis, EPR, resonance Raman, and X-ray absorption spectroscopy, and electrochemical analysis. Addition of the ethoxy group increases the catalytic activity in chemically driven and photocatalytic water oxidation. Thus, the effect of the electron-donating group known for the [Ru(tpy)(bpy)(H2 O)]2+ family is transferable to architectures with a tpy ligand trans to the Ru-oxo unit. Under catalytic conditions, [Ru(EtO-tpy)(pic)2 (H2 O)](NO3 )2 displays new spectroscopic signals tentatively assigned to a peroxo intermediate. Reaction pathways were analyzed by using DFT calculations. [Ru(EtO-tpy)(pic)2 (H2 O)](NO3 )2 is found to be one of the most active catalysts functioning by a water nucleophilic attack mechanism.

Computational Analysis of Structure - Activity Relationships in Highly Active Homogeneous Ruthenium-based Water Oxidation Catalysts.

Linear free energy scaling relationships (LFESRs) and regression analysis may predict the catalytic performance of heterogeneous and recently, homogenous water oxidation catalysts (WOCs). This study analyses twelve homogeneous Ru-based catalysts - some, the most active catalysts studied: the Ru(tpy-R)(QC) and Ru(tpy-R)(4-pic)2 catalysts, where tpy is 2,2:6,2-terpyridine, QC is 8-quinolinecarboxylate and 4-pic is 4-picoline. Typical relationships studied among heterogenous and solid-state catalysts cannot be broadly applied to homogeneous catalysts. This subset of structurally similar catalysts with impressive catalytic activity deserves closer computational and statistical analysis of energetics correlating with measured catalytic activity. We report general methods of LFESR analysis yield insufficiently robust relationships between descriptor variables. However, volcano plot-based analysis grounded in Sabatier's principle reveals ranges of ideal relative energies of the RuIV=O and RuIV-OH intermediates and optimal changes in free energies of water nucleophilic attack on RuV=O. A narrow range of RuIV-OH to RuV=O redox potentials corresponding with the highest catalytic activities suggests facile access to the catalytically competent high-valent RuV=O state, often inaccessible from RuIV=O. Our work introduces experimental oxygen evolution rates into approaches of LFESR and Sabatier principle-based analysis, identifying a narrow yet fertile energetic landscape to bountiful oxygen-evolution activity, leading future rational design.

Do multinuclear 3d metal catalysts achieve O-O bond formation via radical coupling or via water nucleophilic attack? WNA leads the way in [Co4O4]n.

Catalytic water oxidation is a required process for clean energy production based on the concept of artificial photosynthesis. Here, we provide in situ spectroscopic and computational analysis for the closest known photosystem II analog, [Co4O4]n+ ([Co4O4Py4Ac4]0, Py = pyridine and Ac = CH3COO-), which catalyzes electrochemical water oxidation. In situ extended X-ray absorption fine structure detects an ultrashort, CoIV=O (~1.67 Å) moiety, a crucial intermediate for O-O bond formation. Density function theory analyses show that the intermediate has two CoIV centers and a CoIV=O unit of strong radicaloid character sufficient to support a CoIV=O + H2O = Co-OOH + H+ transition, where the carboxyl ligand accepts the proton and the bridging oxygen stabilizes the peroxide via hydrogen bonding. The proposed water nucleophilic attack mechanism accounts for all prior spectroscopic evidence on the Co4O44+ core. Our results are important for the design and development of efficient water oxidation catalysts, which contribute to the ultimate goal of clean energy from artificial photosynthesis.