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The oxygen evolution reaction remains an important bottleneck for widespread implementation of a hydrogen economy. While improvements in the oxygen evolution reaction (OER) can be realized by spin polarizing the reaction intermediates, these methods often rely on applying external magnetic fields to ferromagnetic catalysts or by adsorbing chiral molecules onto the catalyst. Here, we show that the addition of chiral additives to the conductive binder supporting the catalysts en-hances the selectivity for O2 formation and results in exceedingly high mass activities. The results are explained within the context of a statistical model in which the additives are hypothesized to act as a localized chiral bias that enhances radical intermediate coupling. More broadly, these studies illustrate a flexible design motif for improving OER catalysis that persists under different pH conditions, is independent of the choice of catalyst, and can be extrapolated to other chemical reactions.more » « less
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ABSTRACT This review discusses opportunities in chemistry that are enabled by the chiral induced spin selectivity (CISS) effect. First, the review begins with a brief overview of the seminal studies on CISS. Next, we discuss different chiral material systems whose properties can be tailored through chemical means, with a special emphasis on hybrid organic-inorganic layered materials that exhibit some of the largest spin filtering properties to date. Then, we discuss the promise of CISS for chemical reactions and enantioseparation before concluding.more » « less
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Hammes-Schiffer, Sharon (Ed.)Since the initial landmark study on the chiral induced spin selectivity (CISS) effect in 1999, considerable experimental and theoretical efforts have been made to understand the physical underpinnings and mechanistic features of this interesting phenomenon. As first formulated, the CISS effect refers to the innate ability of chiral materials to act as spin filters for electron transport; however, more recent experiments demonstrate that displacement currents arising from charge polarization of chiral molecules lead to spin polarization without the need for net charge flow. With its identification of a fundamental connection between chiral symmetry and electron spin in molecules and materials, CISS promises profound and ubiquitous implications for existing technologies and new approaches to answering age old questions, such as the homochiral nature of life. This review begins with a discussion of the different methods for measuring CISS and then provides a comprehensive overview of molecules and materials known to exhibit CISS-based phenomena before proceeding to identify structure−property relations and to delineate the leading theoretical models for the CISS effect. Next, it identifies some implications of CISS in physics, chemistry, and biology. The discussion ends with a critical assessment of the CISS field and some comments on its future outlook.more » « less
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Abstract Continual progress in technologies that rely on water splitting are often hampered by the slow kinetics associated with the oxygen evolution reaction (OER). Here, we show that the efficiency of top-performing catalysts can be improved, beyond typical thermodynamic considerations, through control over reaction intermediate spin alignment during electrolysis. Spin alignment is achieved using the chiral induced spin selectivity (CISS) effect and the improvement in OER manifests as an increase in Faradaic efficiency, decrease in reaction overpotential, and change in the rate determining step for chiral nanocatalysts over compositionally analogous achiral nanocatalysts. These studies illustrate that a defined spatial orientation of the nanocatalysts is not necessary to exhibit spin selectivity and therefore represent a viable platform for employing the transformative role of chirality in other reaction pathways and processes.more » « less
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This work uses magneto-electrochemical quartz crystal microbalance methods to study the enantiospecific adsorption of chiral molecules onto a ferromagnetic substrate. The effect of solution conditions, pH and solvent isotope composition, indicate that the kinetics of the enantiomeric adsorption depend strongly on the charge state and geometry of the adsorbate, whereas no thermodynamic contributions to enantiospecificity are found. Density functional theory calculations reveal that an interplay between the adsorbate and solvent molecules is important for defining the observed enantiospecific preference with an applied magnetic field, however it remains unclear if intermolecular vibrational couplings contribute to the phenomenon.more » « less
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The chiral induced spin selectivity (CISS) effect, in which the structural chirality of a material determines the preference for the transmission of electrons with one spin orientation over that of the other, is emerging as a design principle for creating next-generation spintronic devices. CISS implies that the spin preference of chiral structures persists upon injection of pure spin currents and can act as a spin analyzer without the need for a ferromagnet. Here, we report an anomalous spin current absorption in chiral metal oxides that manifests a colossal anisotropic nonlocal Gilbert damping with a maximum-to-minimum ratio of up to 1000%. A twofold symmetry of the damping is shown to result from differential spin transmission and backscattering that arise from chirality-induced spin splitting along the chiral axis. These studies reveal the rich interplay of chirality and spin dynamics and identify how chiral materials can be implemented to direct the transport of spin current.more » « less
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Protein voltammetry studies of cytochrome c, immobilized on chiral tripeptide monolayer films, reveal the importance of the electron spin and the film’s homochirality on electron transfer kinetics. Magnetic film electrodes are used to examine how an asymmetry in the standard heterogeneous electron transfer rate constant arises from changes in the electron spin direction and the enantiomer composition of the tripeptide monolayer; rate constant asymmetries as large as 60% are observed. These findings are rationalized in terms of the chiral induced spin selectivity effect and spin-dependent changes in electronic coupling. Lastly, marked differences in the average rate constant are shown between homochiral ensembles, in which the peptide and protein possess the same enantiomeric form, compared to heterochiral ensembles, where the handedness of the peptide layer is opposite to that of the protein, or itself comprises heterochiral building blocks. These data demonstrate a compelling rationale for why nature is homochiral; namely, spin alignment in homochiral systems enables more efficient energy transduction.more » « less
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