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Ethylene is well known as the primary product of CO₂reduction at Cu electrocatalysts using zero-gap membrane electrode assembly cells with gas diffusion cathodes. Other types of Cu electrocatalysts including oxide-derived Cu, CuSn and CuSe yield relatively more C₂oxygenates; however, the mechanisms for C₂product selectivity are not well established. This work considers selectivity trends of Cu-P_0.065, Cu-Sn_0.03, and Cu₂Se electrocatalysts made using a standard one pot synthesis method. Results show that Cu-P_0.065electrocatalysts (Cu^δ+= 0.13) retain ethylene as a primary product with relatively higher Faradaic efficiencies (FE = 43% at 350 mA cm⁻²) than undoped Cu electrocatalysts (FE = 31% at 350 mA cm⁻²) at the same current density. The primary CO₂reduction product at Cu-Sn_0.03(Cu^δ+= 0.27) electrocatalysts shifts to ethanol (FE = 48% at 350 mA cm⁻²) while CO₂reduction at Cu₂Se (Cu^δ+= 0.47) electrocatalysts favor acetate production (FE = 40% at 350 mA cm⁻²). Based on these results, we propose a common acetyl intermediate and a mechanism for selective formation of ethylene, ethanol or acetate based on the degree of partial positive charge (δ⁺) of Cu reaction sites.

 

Quantum interference effects in single-molecule devices can significantly enhance the thermoelectric properties of these devices. However, single-molecule systems have limited utility for power conversion. In this work, we study the effects of destructive quantum interference in molecular junctions on the thermoelectric properties of hybrid, 2-dimensional molecule–nanoparticle monolayers. We study two isomers of benzenedithiol molecules, with either a para or meta configuration for the thiol groups, as molecular interlinkers between gold nanoparticles in the structure. The asymmetrical structure in the meta configuration significantly improves the Seebeck coefficient and power factor over the para configuration. These results suggest that thermoelectric performance of engineered, nanostructured material can be enhanced by harnessing quantum interference effects in the substituent components. 

Inorganic lead-halide perovskite, cesium lead bromide (CsPbBr3), shows outstanding optoelectronic properties. Both solution- and melt-based methods have been proposed for CsPbBr3 crystal growth. The solution-based growth was done at low-temperature, whereas the melt-based growth was done at high-temperature. However, the comparison of optical, physical, and defect states using these two different growth conditions has been scarcely studied. Here, we have compared the thermal and optical properties of solution-grown and melt-grown single crystals of CsPbBr3. Positron Annihilation Lifetime Spectroscopy (PALS) analysis showed that melt-grown crystal has a relatively smaller number of defects than the chemical synthesis method. In addition, crystals grown using the chemical method showed a higher fluorescence lifetime than melt-grown CsPbBr3. 

Noble-transition metal alloys offer emergent optical and electronic properties for near-infrared (NIR) optoelectronic devices. We investigate the optical and electronic properties of CuxPd1−x alloy thin films and their ultrafast electron dynamics under NIR excitation. Ultraviolet photoelectron spectroscopy measurements supported by density functional theory calculations show strong d-band hybridization between the Cu 3d and Pd 4d bands. These hybridization effects result in emergent optical properties, most apparent in the dilute Pd case. Time-resolved terahertz spectroscopy with NIR (e.g., 1550 nm) excitation displays composition-tunable electron dynamics. We posit that the negative peak in the normalized increment of transmissivity (ΔT/T) below 2 ps from dilute Pd alloys is due to non-thermalized hot-carrier generation. On the other hand, Pd-rich alloys exhibit an increase in ΔT/T due to thermalization effects upon ultrafast NIR photoexcitation. CuxPd1−x alloys in the dilute Pd regime may be a promising material for future ultrafast NIR optoelectronic devices.

 

Symmetry-dependent properties such as ferroelectricity are suppressed at room temperature in Pb-free ABO 3 perovskites due to antiferrodistortive dynamics (octahedral rotations/tilts), resulting in the preferential stabilization of centrosymmetric crystals. For this reason, defect engineering (Ca doping, oxygen vacancy, etc. ) has been leveraged to break the symmetry of these crystals by inducing symmetry/structural transitions to modify the local A/B-site environment. This work demonstrates the use of in situ / ex situ photoluminescence spectroscopy to systematically detect symmetry/structural transformations in prototypical ferroelectric ABO 3 perovskites. These baseline optical responses are compared to recently synthesized Ca x Sr 1−x NbO 3 (CSNO) nanocrystals, which undergoes similar ferroelectric/structural phase transitions. Furthermore, the resultant PL response is corroborated with X-ray diffraction (XRD) and absorption spectroscopy (XAS) measurements to confirm the structural changes. This ability to directly monitor the local site symmetry within ABO 3 perovskites via photoluminescence spectroscopy can be used to screen for temperature- and defect-induced ferroelectric transitions.