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.

The chirality-induced spin selectivity (CISS) effect facilitates a paradigm shift for controlling the outcome and efficiency of spin-dependent chemical reactions, for example, photoinduced water splitting. While the phenomenon is established in organic chiral molecules, its emergence in chiral but inorganic, nonmolecular materials is not yet understood. Nevertheless, inorganic spin-filtering materials offer favorable characteristics, such as thermal and chemical stability, over organic, molecular spin filters. Chiral cupric oxide (CuO) thin films can spin polarize (photo)­electron currents, and this capability is linked to the occurrence of the CISS effect. In the present work, chiral CuO films, electrochemically deposited on partially UV-transparent polycrystalline gold substrates, were subjected to deep-UV laser pulses, and the average spin polarization of photoelectrons was measured in a Mott scattering apparatus. By energy resolving the photoelectrons and changing the photoexcitation geometry, the energy distribution and spin polarization of the photoelectrons originating from the Au substrate could be distinguished from those arising from the CuO film. The findings reveal that the spin polarization is energy dependent and, furthermore, indicate that the measured polarization values can be rationalized as a sum of an intrinsic spin polarization in the chiral oxide layer and a contribution via CISS-related spin filtering of electrons from the Au substrate. The results support efforts toward a rational design of further spin-selective catalytic oxide materials.

Monolayers of chiral molecules can preferentially transmit electrons with a specific spin orientation, introducing chiral molecules as efficient spin filters. This phenomenon is established as chirality-induced spin selectivity (CISS) and was demonstrated directly for the first time in self-assembled monolayers (SAMs) of double-stranded DNA (dsDNA) 1. Here, we discuss SAMs of double-stranded peptide nucleic acid (dsPNA) as a system which allows for systematic investigations of the influence of various molecular properties on CISS. In photoemission studies, SAMs of chiral, γ-modified PNA show significant spin filtering of up to P = (24.4 ± 4.3)% spin polarization. The polarization values found in PNA lacking chiral monomers are considerably lower at about P = 12%. The results confirm that the preferred spin orientation is directly linked to the molecular handedness and indicate that the spin filtering capacity of the dsPNA helices might be enhanced by introduction of chiral centers in the constituting peptide monomers.

In this short overview we discuss the manifestation of the chirality-induced spin selectivity (CISS) effect in photoelectron spectroscopy experiments with direct spin analysis. Various systems, from the initially investigated monolayers of molecular biosystems and organic heptahelicene to recent chirally grown solid oxide films, are evaluated. High spin polarization values of up to P = 60 % have been observed for samples at room temperature. For all classes it was shown that the longitudinal spin orientation changes sign with a change of the enantiomeric form. Recent advances allow to distinguish the contributions of electrons with different kinetic energies to the electron spin polarization, and thus to distinguish the CISS effect from bulk contributions to the spin originating from different mechanisms.