Project description:Anodic oxygen evolution reaction (OER) is recognized as kinetic bottleneck in water electrolysis. Transition metal sites with high valence states can accelerate the reaction kinetics to offer highly intrinsic activity, but suffer from thermodynamic formation barrier. Here, we show subtle engineering of highly oxidized Ni4+ species in surface reconstructed (oxy)hydroxides on multicomponent FeCoCrNi alloy film through interatomically electronic interplay. Our spectroscopic investigations with theoretical studies uncover that Fe component enables the formation of Ni4+ species, which is energetically favored by the multistep evolution of Ni2+→Ni3+→Ni4+. The dynamically constructed Ni4+ species drives holes into oxygen ligands to facilitate intramolecular oxygen coupling, triggering lattice oxygen activation to form Fe-Ni dual-sites as ultimate catalytic center with highly intrinsic activity. As a result, the surface reconstructed FeCoCrNi OER catalyst delivers outstanding mass activity and turnover frequency of 3601 A gmetal-1 and 0.483 s-1 at an overpotential of 300 mV in alkaline electrolyte, respectively.
Project description:Molecular catalysts are known for their high activity and tunability, but their solubility and limited stability often restrict their use in practical applications. Here we describe how a molecular iridium catalyst for water oxidation directly and robustly binds to oxide surfaces without the need for any external stimulus or additional linking groups. On conductive electrode surfaces, this heterogenized molecular catalyst oxidizes water with low overpotential, high turnover frequency and minimal degradation. Spectroscopic and electrochemical studies show that it does not decompose into iridium oxide, thus preserving its molecular identity, and that it is capable of sustaining high activity towards water oxidation with stability comparable to state-of-the-art bulk metal oxide catalysts.
Project description:The optoelectronic properties of metal-halide perovskites (MHPs) are affected by lattice fluctuations. Using ultrafast pump-probe spectroscopy, we demonstrate that in state-of-the-art mixed-cation MHPs ultrafast photo-induced bandgap narrowing occurs with a linear to super-linear dependence on the excited carrier density ranging from 1017 cm-3 to above 1018 cm-3. Time-domain terahertz spectroscopy reveals carrier localization increases with carrier density. Both observations, the anomalous dependence of the bandgap narrowing and the increased carrier localization can be rationalized by photo-induced lattice fluctuations. The magnitude of the photo-induced lattice fluctuations depends on the intrinsic instability of the MHP lattice. Our findings provide insight into ultrafast processes in MHPs following photoexcitation and thus help to develop a concise picture of the ultrafast photophysics of this important class of emerging semiconductors.
Project description: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.
Project description:A molecular water oxidation catalyst, [Ru(tpy)(dcbpy)(OH2)](ClO4)2 (tpy = 2,2':6',2''-terpyridine, dcbpy = 2,2'-bipyridine-5,5'-dicarboxylic acid) [1], has been incorporated into FTO-grown thin films of UiO-67 (UiO = University of Oslo), by post-synthetic ligand exchange. Cyclic voltammograms (0.1 M borate buffer at pH = 8.4) of the resulting UiO67-[RuOH2]@FTO show a reversible wave associated with the RuIII/II couple in the anodic scan, followed by a large current response that arises from electrocatalytic water oxidation beyond 1.1 V vs. Ag/AgCl. Water oxidation can be observed at an applied potential of 1.5 V over the timescale of hours with a current density of 11.5 ?A cm-2. Oxygen evolution was quantified in situ over the course of the experiment, and the Faradaic efficiency was calculated as 82%. Importantly, the molecular integrity of [1] during electrocatalytic water oxidation is maintained even on the timescale of hours under turnover conditions and applied voltage, as evidenced by the persistence of the wave associated with the RuIII/II couple in the CV. This experiment highlights the capability of metal organic frameworks like UiO-67 to stabilize the molecular structure of catalysts that are prone to form higher clusters in homogenous phase.
Project description:Electrochemical (EC) and photoelectrochemical (PEC) water splitting represent promising strategies for renewable energy conversion and fuel production and require design of efficient catalysts for the oxygen evolution reaction (OER). Herein, we report the synthesis of two-dimensional (2D) Co-based metal organic framework (Co-MOF) nanosheets and their bifunctional catalytic properties for both EC and PEC OER. Benefiting from the large surface area and abundant isolated metal active sites, the Co-MOF nanosheets exhibited excellent OER activity and stability. The efficient electron-hole generation and separation of the nanosheets, owing to dimensional confinement, contributed to an improved visible light response in PEC OER. This study presents a new strategy to design EC/PEC bifunctional catalyst utilizing unique structural and electronic features of 2D MOF.
Project description:The experimental realization of p-orbital systems is desirable because p-orbital lattices have been proposed theoretically to host strongly correlated electrons that exhibit exotic quantum phases. Here, we synthesize a two-dimensional Fe-coordinated bimolecular metal-organic framework which constitutes a honeycomb lattice of 1,4,5,8,9,12-hexaazatriphenylene molecules and a Kagome lattice of 5,15-di(4-pyridyl)-10,20-diphenylporphyrin molecules on a Au(111) substrate. Density-functional theory calculations show that the framework features multiple well-separated spin-polarized Kagome bands, namely Dirac cone bands and Chern flat bands, near the Fermi level. Using tight-binding modelling, we reveal that these bands are originated from two effects: the low-lying molecular orbitals that exhibit p-orbital characteristics and the honeycomb-Kagome lattice. This study demonstrates that p-orbital Kagome bands can be realized in metal-organic frameworks by using molecules with molecular orbitals of p-orbital like symmetry.
Project description:Splitting of water into hydrogen and oxygen has become a strategic research topic. In the two semi-reactions of water splitting, water oxidation is preferred to the four-electron-transfer process with a higher overpotential (η) and is the decisive step in water splitting. Therefore, efficient water oxidation catalysts must be developed. IrO x and RuO x catalysts are currently the most efficient catalysts in water oxidation. However, the limited reserve and high prices of precious metals, such as Ir and Ru, limit future large-scale industrial production of water oxidation catalysts. In this study, we tune inert Ni-foam into highly active NiOOH/FeOOH heterostructures as water oxidation catalysts via three-step strategy (surface acid-treating, electroplating, and electrooxidation). NiOOH/FeOOH heterostructures as water oxidation catalysts only require η of 257 mV to reach a current density of 10 mA cm-2, which is superior to that of IrO2/Ni-foam (280 mV). The high electrochemically active surface area (72.50 cm2) and roughness factor demonstrate abundant interfaces in NiOOH/FeOOH heterostructures, thus accelerating water oxidation activity. The small value (4.8 Ω cm2) of charge transfer resistance (R ct) indicate that fast electronic exchange occurs between NiOOH/FeOOH heterostructures catalyst and reaction of water oxidation. Hydrogen-to-oxygen volume ratios (approximately 2:1) indicate an almost overall water splitting by the double-electrode system. Faraday efficiency of H2 or O2 is close to 90% at 2:1 hydrogen-to-oxygen volume ratio. NiOOH/FeOOH heterostructures exhibit good stability. The results provide significance in fundamental research and practical applications in solar water splitting, artificial photoelectrochemical cells, and electrocatalysts.
Project description:Significance Symmetries are increasingly shown to play various key roles determining the possible phases in condensed matter systems. We study bosonic particles (including electron Cooper pairs) living on the vertices of a honeycomb lattice at a density of 1/2 per site. Here the honeycomb symmetries forbid the usual fermionic band insulating state, and the conventional Mott (“strongly interacting”) insulator involves a whole number of particles frozen on each site, suggesting that featureless (fully symmetric) insulators might not exist in this system. Nevertheless, we explicitly construct quantum states and demonstrate that they are examples of featureless insulators on the honeycomb lattice at 1/2 site filling, with a procedure generalizing to lattices with symmorphic symmetry groups. Within the Landau paradigm, phases of matter are distinguished by spontaneous symmetry breaking. Implicit here is the assumption that a completely symmetric state exists: a paramagnet. At zero temperature such quantum featureless insulators may be forbidden, triggering either conventional order or topological order with fractionalized excitations. Such is the case for interacting particles when the particle number per unit cell, f, is not an integer. However, can lattice symmetries forbid featureless insulators even at integer f? An especially relevant case is the honeycomb (graphene) lattice—where free spinless fermions at
Project description:Because of their high tunability and surface area, metal-organic frameworks (MOFs) show great promise as supports for metal nanoparticles. Depending on the synthesis route, MOFs may contain defects. Here, we show that highly crystalline MIL-100(Fe) and disordered Basolite® F300, with identical iron 1,3,5-benzenetricarboxylate composition, exhibit very divergent properties when used as a support for Pd nanoparticle deposition. While MIL-100(Fe) shows a regular MTN-zeotype crystal structure with two types of cages, Basolite® F300 lacks long-range order beyond 8 Å and has a single-pore system. The medium-range configurational linker-node disorder in Basolite® F300 results in a reduced number of Lewis acid sites, yielding more hydrophobic surface properties compared to hydrophilic MIL-100(Fe). The hydrophilic/hydrophobic nature of MIL-100(Fe) and Basolite® F300 impacts the amount of Pd and particle size distribution of Pd nanoparticles deposited during colloidal synthesis and dry impregnation methods, respectively. It is suggested that polar (apolar) solvents/precursors attractively interact with hydrophilic (hydrophobic) MOF surfaces, allowing tools at hand to increase the level of control over, for example, the nanoparticle size distribution.