Mixed X-Site Formate-Hypophosphite Hybrid Perovskites.

Following the recent discovery of a new family of hybrid ABX3 perovskites where X=(H2 POO)- (hypophosphite), this work reports a facile synthesis for mixed X-site formate perovskites of composition [GUA]Mn(HCOO)3-x (H2 POO)x , with two crystallographically distinct, partially ordered intermediate phases with x=0.84 and 1.53, corresponding to ca. 30 and 50 mol % hypophosphite, respectively. These phases are characterised by single-crystal XRD and solid-state NMR spectroscopy, and their magnetic properties are reported.

Enhancing the capacity of supercapacitive swing adsorption CO2 capture by tuning charging protocols.

Supercapacitive swing adsorption (SSA) is a recently discovered electrochemically driven CO2 capture technology that promises significant efficiency improvements over traditional methods. A limitation of this approach is the relatively low CO2 adsorption capacity, and the underlying molecular mechanisms of SSA remain poorly understood, hindering optimization. Here we present a new device architecture for simultaneous electrochemical and gas-adsorption measurements, and use it to investigate the effects of charging protocols on SSA performance. We show that altering the voltage applied to charge the SSA device can significantly improve performance. Charging the gas-exposed electrode positively rather than negatively increases CO2 adsorption capacity and causes CO2 desorption rather than adsorption with charging. We also show that switching the voltage between positive and negative values further increases CO2 capacity. Previously proposed mechanisms of the SSA effect fail to explain these phenomena, so we present a new mechanism based on movement of CO2-derived species into and out of electrode micropores. Overall, this work advances our knowledge of electrochemical CO2 adsorption by supercapacitors, potentially leading to devices with increased uptake capacity and efficiency.

Hypophosphite hybrid perovskites: a platform for unconventional tilts and shifts.

Following the recent discovery of the [A]Mn(H2POO)3 (H2POO- = hypophosphite) perovskite family, we report the A = [NH2(CH3)2]+ (dimethylammonium, DMA) member. This phase shows an unusually large unit cell due to the position of the A-site cation within the perovskite cage windows rather than the centre, as is the norm. We discuss the tendency of the hypophosphite perovskite skeleton to accommodate differently shaped A-site cations through the generation of unconventional tilts and columnar shifts, then enumerate these tilts and shifts for all known [A]Mn(H2POO)3 phases.