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We identified the perovskite oxides LaMn0.5Ni0.5O3 (L2MN), Gd0.5La0.5Mn0.5Ni0.5O3 (GLMN), and GdMn0.5Ni0.5O3 (G2MN) as candidate solar thermal chemical hydrogen (STCH) redox mediators from their density functional theory (DFT)-computed electronic and oxygen vacancy properties following a high-throughput computational screening of AA′BB′O6 compositions that are likely to form as perovskites and split water. At a thermal reduction temperature of 1350 °C and a water splitting temperature of 850 °C, the L2MN and GLMN perovskites produced ∼65 μmol g–1 of hydrogen per cycle with no phase degradation over three redox cycles at 40 mol % steam, while the G2MN perovskite did not produce STCH under these conditions. When reoxidized by exposure to a gas flow with a H2O:H2 molar ratio of 1333:1, which represents operating conditions where the thermodynamic driving force of water splitting is lowered by orders of magnitude relative to 40 mol % steam, the L2MN and GLMN perovskites each produced ∼35 μmol g–1 of hydrogen per cycle. Guided by DFT, we propose that L2MN and GLMN’s STCH activities arise from B-site cation antisite defects that facilitate oxygen vacancy formation and thus redox cycling, whereas the synthesized G2MN has few antisite defects and is therefore inactive for STCH. 

Continuous vibrating spatial particle ALD reactors were developed to achieve high powder throughput while minimizing reactor footprint. Unlike fluidized bed reactors, continuous vibrating spatial particle ALD reactors operate below fluidization, using linear vibration to convey particles through alternating regions of precursor gas. Fine powder convection in these vibrating bed reactors is still not well understood, so cohesive discrete element- method (DEM) simulations were performed to investigate the solids flow behavior. Using a Fast Fourier Transform(FFT) algorithm, we constructed a sum-of-sines model for the reactor kinematics based on accelerometer data. Accelerometer results and DEM simulations revealed the role of high-frequency excitations and need for backsliding and sticking avoidance in horizontal conveyors at low-g accelerations. From these observations, we propose a novel sawtooth excitation to enable convection of cohesive fine powders at low flow velocities. The model results were compared to data from an in-house continuous vibrating spatial particle ALD reactor.