The positions of electronic band edges are one important metric for determining a material's capability to function in a solar energy conversion device that produces fuels from sunlight. In particular, the position of the valence band maximum (conduction band minimum) must lie lower (higher) in energy than the oxidation (reduction) reaction free energy in order for these reactions to be thermodynamically favorable. We present first principles quantum mechanics calculations of the band edge positions in five transition metal oxides and discuss the feasibility of using these materials in photoelectrochemical cells that produce fuels, including hydrogen, methane, methanol, and formic acid. The band gap center is determined within the framework of DFT+U theory. The valence band maximum (conduction band minimum) is found by subtracting (adding) half of the quasiparticle gap obtained from a non-self-consistent GW calculation. The calculations are validated against experimental data where possible; results for several materials including manganese(II) oxide, iron(II) oxide, iron(III) oxide, copper(I) oxide and nickel(II) oxide are presented.

Fe-containing transition-metal (oxy)hydroxides are highly active oxygen-evolution reaction (OER) electrocatalysts in alkaline media and ubiquitously form across many materials systems. The complexity and dynamics of the Fe sites within the (oxy)hydroxide have slowed understanding of how and where the Fe-based active sites form—information critical for designing catalysts and electrolytes with higher activity and stability. We show that where/how Fe species in the electrolyte incorporate into host Ni or Co (oxy)hydroxides depends on the electrochemical history and structural properties of the host material. Substantially less Fe is incorporated from Fe-spiked electrolyte into Ni (oxy)hydroxide at anodic potentials, past the nominally Ni^2+/3+ redox wave, compared to during potential cycling. The Fe adsorbed under constant anodic potentials leads to impressively high per-Fe OER turn-over frequency (TOF_Fe) of ~40 s⁻¹ at 350 mV overpotential which we attribute to under-coordinated “surface” Fe. By systematically controlling the concentration of surface Fe, we find TOF_Fe increases linearly with the Fe concentration. This suggests a changing OER mechanism with increased Fe concentration, consistent with a mechanism involving cooperative Fe sites in FeO_x clusters.

Metal-organic frameworks (MOFs) are commended as photocatalysts for H₂ evolution and CO₂ reduction as they combine light-harvesting and catalytic functions with excellent reactant adsorption capabilities. For dynamic processes in liquid phase, the accessibility of active sites becomes a critical parameter as reactant diffusion is limited by the inherently small micropores. Our strategy is to introduce additional mesopores by selectively removing one ligand in mixed-ligand MOFs via thermolysis. Here we report photoactive MOFs of the MIL-125-Ti family with two distinct mesopore architectures resembling either large cavities or branching fractures. The ligand removal is highly selective and follows a 2-step process tunable by temperature and time. The introduction of mesopores and the associated formation of new active sites have improved the HER rates of the MOFs by up to 500%. We envision that this strategy will allow the purposeful engineering of hierarchical MOFs and advance their applicability in environmental and energy technologies.

Nickel-, cobalt-, and iron-based (oxy)hydroxides comprise the most-commonly studied electrocatalysts for the oxygen-evolution reaction (OER) in alkaline solution. A fundamental understanding of composition-structure-activity relationships for mixed-metal Ni-Co and Ni-Co-Fe (oxy)hydroxides is important to guide the design of advanced OER catalysts. Here we use cyclic voltammetry, chronopotentiometry, inductively-coupled plasma-optical emission spectroscopy, and in situ electrical conductivity measurements to characterize the properties and activity of various compositions of Ni-Co-Fe (oxy)hydroxides prepared by cathodic co-electrodeposition. Consistent with previous studies, we find Fe is essential for the mixed-metal (oxy)hydroxides to achieve high OER activity. In the rigorous absence of Fe (achieved by using specially cleaned electrolytes), the most-active Ni-Co (oxy)hydroxide composition has an OER turn-over frequency only twice that of pure Co (oxy)hydroxide, suggesting minimal synergism between the two metals. The addition of Co to Ni-Fe (oxy)hydroxides shifts the onset of electrical conductivity to lower potentials, but has little effect on the intrinsic OER activity, with the most-active Ni-Co-Fe (oxy)hydroxide having an OER turn-over frequency only ~ 1.5 times that of the Ni-Fe (oxy)hydroxides. The magnitudes of the electrical conductivities are similar for all the compositions measured. Density-functional-theory-calculated projected density of states show a significant contribution of all chemical elements at the valence band edge of the mixed-metal oxyhydroxide electronic structure, demonstrating significant electronic hybridization between the elements. The calculations suggest the involvement of all the elements in modulating the electronic structure at putative Fe-based active sites that are probably located at edges or defects in the two-dimensional oxyhydroxide sheets. Open image in new window