Rapidly determining the 3D structure of proteins by surface-enhanced Raman spectroscopy.

Despite great advances in protein structure analysis, label-free and ultrasensitive methods to obtain the natural and dynamic three-dimensional (3D) structures are still urgently needed. Surface-enhanced Raman spectroscopy (SERS) can be a good candidate, whereas the complexity originated from the interactions between the protein and the gradient surface electric field makes it extremely challenging to determine the protein structure. Here, we propose a deciphering strategy for accurate determination of 3D protein structure from experimental SERS spectra in seconds by simply summing SERS spectra of isolated amino acids in electric fields of different strength with their orientations in protein. The 3D protein structure can be reconstructed by comparing the experimental spectra obtained in a well-defined gap-mode SERS configuration with the simulated spectra. The gradient electric field endows SERS with a unique advantage to section biomolecules with atomic precision, which makes SERS a competent tool for monitoring biomolecular events under physiological conditions.

Interfacial Synergy between the Cu Atomic Layer and CeO2 Promotes CO Electrocoupling to Acetate.

Cu is considered to be an effective electrocatalyst in CO/CO2 reduction reactions (CORR/CO2RR) because of its C-C coupling into C2+ products, but it still remains a formidable challenge to rationally design Cu-based catalysts for highly selective CO/CO2 reduction to C2+ liquid products such as acetate. We here demonstrate that spraying atomically layered Cu atoms onto CeO2 nanorods (Cu-CeO2) can lead to a catalyst with an enhanced acetate selectivity in CORR. Owing to the existence of oxygen vacancies (Ov) in CeO2, the layer of Cu atoms at interface coordinates with Ce atoms in the form of Cu-Ce (Ov), as a result of strong interfacial synergy. The Cu-Ce (Ov) significantly promotes the adsorption and dissociation of H2O, which further couples with CO to selectively produce acetate as the dominant liquid product. In the current density range of 50-150 mA cm-2, the Faradaic efficiencies (FEs) of acetate are over 50% with a maximum value of 62.4%. In particular, the turnover frequency of Cu-CeO2 reaches 1477 h-1, surpassing that of Cu nanoparticle-decorated CeO2 nanorods, bare CeO2 nanorods, as well as other existing Cu-based catalysts. This work advances the rational design of high-performance catalysts for CORR to highly value-added products, which may attract great interests in diverse fields including materials science, chemistry, and catalysis.

Recent advances in plasmon-enhanced Raman spectroscopy for catalytic reactions on bifunctional metallic nanostructures.

Metallic nanostructures exhibit superior catalytic performance for diverse chemical reactions and the in-depth understanding of reaction mechanisms requires versatile characterization methods. Plasmon-enhanced Raman spectroscopy (PERS), including surface-enhanced Raman spectroscopy (SERS), shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS), and tip-enhanced Raman spectroscopy (TERS), appears as a powerful technique to characterize the Raman fingerprint information of surface species with high chemical sensitivity and spatial resolution. To expand the range of catalytic reactions studied by PERS, catalytically active metals are integrated with plasmonic metals to produce bifunctional metallic nanostructures. In this minireview, we discuss the recent advances in PERS techniques to probe the chemical reactions catalysed by bifunctional metallic nanostructures. First, we introduce different architectures of these dual-functionality nanostructures. We then highlight the recent works using PERS to investigate important catalytic reactions as well as the electronic and catalytic properties of these nanostructures. Finally, we provide some perspectives for future PERS studies in this field.

Probing the Local Generation and Diffusion of Active Oxygen Species on a Pd/Au Bimetallic Surface by Tip-Enhanced Raman Spectroscopy.

Active oxygen species (AOS) play key roles in many important catalytic reactions relevant to clean energy and environment. However, it remains challenging to characterize the active sites for producing AOS and to image the surface properties of AOS, especially on multicomponent metallic catalyst surfaces. Herein, we utilize tip-enhanced Raman spectroscopy (TERS) to probe the local generation and diffusion of OH radicals on a Pd/Au(111) bimetallic catalyst surface. The reactive OH radicals can be catalytically generated from hydrogen peroxide (H2O2) at the metal surface, which then oxidizes the surface adsorbed thiolate, a reactant that is used as the TERS probe. By TERS imaging of the spatial distribution of unreacted thiolate molecules, we demonstrate that the Pd surface is active for generation of OH radicals and the Pd step edge shows much higher activity than the Pd terrace, whereas the Au surface is inactive. Furthermore, we find that the locally generated OH radicals at the Pd step edge could diffuse to both the Au and the Pd surface sites to induce oxidative reactions, with a diffusion length estimated to be about 5.4 nm. Our TERS imaging with few-nanometer spatial resolution not only unravels the active sites but also characterizes in real space the diffusion behavior of OH radicals. The results are highly valuable to understand AOS-triggered catalytic reactions. The strategy of using reactants with large Raman cross sections as TERS probes may broaden the application of TERS for studying catalysis with reactive small molecules.