Controlling Chemical Selectivity in Electrocatalysis with Chiral CuO-Coated Electrodes

Abstract

This work demonstrates the chiral-induced spin selectivity effect for inorganic copper oxide films and exploits it to enhance the chemical selectivity in electrocatalytic water splitting. Chiral CuO films are electrodeposited on a polycrystalline Au substrate, and their spin filtering effect on electrons is demonstrated using Mott polarimetry analysis of photoelectrons. CuO is known to act as an electrocatalyst for the oxygen evolution reaction; however, it also generates side products such as H2O2. We show that chiral CuO is selective for O2; H2O2 generation is strongly suppressed on chiral CuO but is present with achiral CuO. The selectivity is rationalized in terms of the electron spin-filtering properties of the chiral CuO and the spin constraints for the generation of triplet oxygen. These findings represent an important step toward the development of all-inorganic chiral materials for electron spin filtering and the creation of efficient, spin-selective (photo)­electrocatalysts for water splitting.

Organic-to-inorganic structural chirality transfer in a 2D hybrid perovskite and impact on Rashba-Dresselhaus spin-orbit coupling

“…These structural insights, coupled with theoretical findings in our work, enable the discovery and design of an emerging class of multifunctional hybrid systems with an amalgam of semiconducting, chiroptical, and spin-dependent properties. Indeed, the combination of chiral induced spin selectivity of chiral organic molecules [56][57][58][59][60][61][62] and an intrinsic RD spin-splitting in the inorganic framework is a hitherto unexplored aspect unique to 2D chiral HOIPs and might have practical implications in future HOIP-based spintronics. Further, the structural chirality transfer and ensuing lowering of symmetry within the inorganic sublattice opens up a gateway to other emergent properties such as nonlinear light-matter interactions and piezo-/ferroelectricity, not just in 2D HOIPs but also in related diverse low-dimensional metal halide hybrids.…”

Porous Cupric Oxide: Efficient Photocathode for Photoelectrochemical Water Splitting

“…All the above‐mentioned features make CuO as an efficient visible light active photocathode. Although there are only a few reports on the investigation of photoelectrochemical behaviour of CuO as an efficient semiconductor for solar hydrogen evolution reaction …”

Manipulating spin polarization of titanium dioxide for efficient photocatalysis

“…Notably, the induced spin polarization by chiral molecules or chiral films (on TiO 2 , Fe 3 O 4 , CuO, etc.) can improve the performances of electrocatalytic and photoelectrochemical (PEC) water splitting [17][18][19][20] , by means of suppressing the formation of hydrogen peroxide (H 2 O 2 ) and favoring the high yield of paramagnetic triplet molecule oxygen (via the parallel spin alignment of oxygen atoms) due to the chiralinduced spin selectivity (CISS) effect [21][22][23] . Very recently, the external magnetic field has been applied to strengthen the spinrestricted water oxidation process by accelerating the parallel alignment of oxygen radicals during the formation of O-O bond 24 .…”