Search

The carbon-carbon (C-C) bond formation is essential for the electroconversion of CO 2 into high-energy-density C 2+ products, and the precise coupling pathways remain controversial. Although recent computational investigations have proposed that the OC-COH coupling pathway is more favorable in specific reaction conditions than the well-known CO dimerization pathway, the experimental evidence is still lacking, partly due to the separated catalyst design and mechanistic/spectroscopic exploration. Here, we employ density functional theory calculations to show that on low-coordinated copper sites, the *CO bindings are strengthened, and the adsorbed *CO coupling with their hydrogenation species, *COH, receives precedence over CO dimerization. Experimentally, we construct a fragmented Cu catalyst with abundant low-coordinated sites, exhibiting a 77.8% Faradaic efficiency for C 2+ products at 300 mA cm -2 . With a suite of in situ spectroscopic studies, we capture an *OCCOH intermediate on the fragmented Cu surfaces, providing direct evidence to support the OC-COH coupling pathway. The mechanistic insights of this research elucidate how to design materials in favor of OC-COH coupling toward efficient C 2+ production from CO 2 reduction.

Plasmonic nanoparticles are ideal candidates for hot-electron-assisted applications, but their narrow resonance region and limited hotspot number hindered the energy utilization of broadband solar energy. Inspired by tree branches, we designed and chemically synthesized silver fractals, which enable self-constructed hotspots and multiple plasmonic resonances, extending the broadband generation of hot electrons for better matching with the solar radiation spectrum. We directly revealed the plasmonic origin, the spatial distribution, and the decay dynamics of hot electrons on the single-particle level by using ab initio simulation, dark-field spectroscopy, pump-probe measurements, and electron energy loss spectroscopy. Our results show that fractals with acute tips and narrow gaps can support broadband resonances (400-1100 nm) and a large number of randomly distributed hotspots, which can provide unpolarized enhanced near field and promote hot electron generation. As a proof-of-concept, hot-electron-triggered dimerization of p -nitropthiophenol and hydrogen production are investigated under various irradiations, and the promoted hot electron generation on fractals was confirmed with significantly improved efficiency.

Here we report the wet-chemical synthesis of asymmetric one-dimensional (1D) silver "nanocarrot" structures that exhibit mixed twins and stacking fault domains along the <111> direction. Oriented attachment is the dominant mechanism for anisotropic growth. Multipolar plasmon resonances up to fourth order were measured by optical extinction spectroscopy and electron energy-loss spectroscopy (EELS) and are in agreement with theoretical calculations. Compared with those of symmetric 1D nanostructures of similar length, the dipole modes of the nanocarrots show a clear red shift, and the EELS maps show an asymmetric distribution of the resonant plasmonic fields and a compression of the resonance node spacing toward the tail. In addition, increasing the length of the nanocarrots causes an increase in the intensity and a steady red shift of the longitudinal surface plasmon resonance peaks. The silver nanocarrots also show very high sensitivity to the refractive index of their environment (890 ± 87 nm per refractive index unit).

The sensitivity and the limit of detection of Raman sensors are limited by the extremely small scattering cross section of Raman labels. Silver nanorice antennae are coupled with a patterned gold triangle nanoarray chip to create spatially broadened plasmonic "hot spots", which enables a large density of Raman labels to experience strong local electromagnetic field. Finite difference time domain simulations have confirmed that the quasi-periodic structure increases the intensity and the area of the surface plasmon resonance (SPR), which enhances the surface-enhanced Raman scattering (SERS) signal significantly. The SERS signal of the nanorice/DNA/nanoarray chip is compared with that of the nanorice/DNA/film chip. The SERS signal is greatly enhanced when the Ag nanorices are coupled to the periodic Au nanoarray instead of the planar film chip. The resulting spatially broadened SPR field enables the SERS biosensor with a limit of detection of 50 aM toward hepatitis B virus DNA with the capability of discriminating a single-base mutant of DNA. This sensing platform can be extended to detect other chemical species and biomolecules such as proteins and small molecules.

High-yield uniform silver nanorices were synthesized by a facile polyol process without the introduction of shape-selected seeds. Nanorices exhibit two plasmon resonance peaks in the visible and near-infrared regions respectively due to their anisotropy. XRD patterns demonstrated the HCP phase coexists with the FCC phase in nanorices. The novel structure of nanorices was characterized by TEM study which shows that the intergrowth of FCC and a small amount of HCP phase, nanoscale FCC (111) twinning structure, and multimodulated structures formed by a complicated stacking sequence along the long axis direction. The correlation between morphology and microstructure is discussed.