Yuanjie Pang

Enhanced electrocatalytic CO2 reduction via field-induced reagent concentration

Electrochemical reduction of carbon dioxide (CO2) to carbon monoxide (CO) is the first step in the synthesis of more complex carbon-based fuels and feedstocks using renewable electricity. Unfortunately, the reaction suffers from slow kinetics owing to the low local concentration of CO2 surrounding typical CO2 reduction reaction catalysts. Alkali metal cations are known to overcome this limitation through non-covalent interactions with adsorbed reagent species, but the effect is restricted by the solubility of relevant salts. Large applied electrode potentials can also enhance CO2 adsorption, but this comes at the cost of increased hydrogen (H2) evolution. Here we report that nanostructured electrodes produce, at low applied overpotentials, local high electric fields that concentrate electrolyte cations, which in turn leads to a high local concentration of CO2 close to the active CO2 reduction reaction surface. Simulations reveal tenfold higher electric fields associated with metallic nanometre-sized tips compared to quasi-planar electrode regions, and measurements using gold nanoneedles confirm a field-induced reagent concentration that enables the CO2 reduction reaction to proceed with a geometric current density for CO of 22 milliamperes per square centimetre at −0.35 volts (overpotential of 0.24 volts). This performance surpasses by an order of magnitude the performance of the best gold nanorods, nanoparticles and oxide-derived noble metal catalysts. Similarly designed palladium nanoneedle electrocatalysts produce formate with a Faradaic efficiency of more than 90 per cent and an unprecedented geometric current density for formate of 10 milliamperes per square centimetre at −0.2 volts, demonstrating the wider applicability of the field-induced reagent concentration concept.

Optical Trapping of a Single Protein

We experimentally demonstrate the optical trapping of a single bovine serum albumin (BSA) molecule that has a hydrodynamic radius of 3.4 nm, using a double-nanohole in an Au film. The strong optical force in the trap not only stably traps the protein molecule but also unfolds it. The unfolding of the BSA is confirmed by experiments with changing optical power and with changing solution pH. The detection of the trapping event has a signal-to-noise ratio of 33, which shows that the setup is extremely sensitive to detect the presence of a protein, even at the single molecule level.

Hyperspectral nanoscale imaging on dielectric substrates with coaxial optical antenna scan probes

An important goal in nano science is to unlock previously inaccessible physics and dynamics within nanoscale systems by combining the efficient nanoscale field confinement/optical resolution (∼10 nm) of optical antennae and the ultrafast temporal resolution (fs) inherent in optical studies with the capabilities of modern scanning probe techniques. Here we report on a significant step toward this goal using a novel nanofabricated coaxial antenna tip capable of recording useful Raman spectra in ∼50 ms to acquire 256 by 256 pixel images on dielectric substrates with a full spectrum at each pixel.

Optical Trapping of 12 nm Dielectric Spheres Using Double-Nanoholes in a Gold Film

Optical tweezers have found many applications in biology, but for reasonable intensities, conventional traps are limited to particles >100 nm in size. We use a double-nanohole in a gold film to experimentally trap individual nanospheres, including 20 nm polystyrene spheres and 12 nm silica spheres, at a well-defined trapping point. We present statistical studies on the trapping time, showing an exponential dependence on the optical power. Trapping experiments are repeated for different particles and several nanoholes with different gap dimensions. Unusually, smaller particles can be more easily trapped than larger ones with the double-nanohole. The 12 nm silica sphere has a size and a refractive index comparable to the smallest virus particles and has a spherical shape which is the worst case scenario for trapping.

Extraordinary optical transmission brightens near-field fiber probe.

Near-field scanning optical microscopy (NSOM) offers high optical resolution beyond the diffraction limit for various applications in imaging, sensing, and lithography; however, for many applications the very low brightness of NSOM aperture probes is a major constraint. Here, we report a novel NSOM aperture probe that gives a 100× higher throughput and 40× increased damage threshold than conventional near-field aperture probes. These brighter probes facilitate near-field imaging of single molecules with apertures as small as 45 nm in diameter. We achieve this improvement by nanostructuring the probe and by employing a novel variant of extraordinary optical transmission, relying solely on a single aperture and a coupled waveguide. Comprehensive electromagnetic simulations show good agreement with the measured transmission spectra. Due to their significantly increased throughput and damage threshold, these resonant configuration probes provide an important step forward for near-field applications.

Optical trapping of individual human immunodeficiency viruses in culture fluid reveals heterogeneity with single-molecule resolution

Optical tweezers use the momentum of photons to trap and manipulate microscopic objects contact-free in three dimensions. Although this technique has been widely used in biology and nanotechnology to study molecular motors, biopolymers and nanostructures, its application in viruses has been very limited largely due to the small size of these nanoparticles. Using optical tweezers that can simultaneously resolve two-photon fluorescence at single-molecule level, here we show that individual HIV-1 can be optically trapped and manipulated, which allows multi-parameter analysis of single virions in culture fluid under native conditions. We show that individual HIV-1 differs in the numbers of envelope glycoproteins by more than one order of magnitude, which implies substantial heterogeneity of these virions in transmission and infection at single-particle level. Analogous to flow cytometry for cells, this fluid-based technique may allow ultrasensitive detection, multi-parameter analysis and sorting of viruses and other nanoparticles in biological fluid with single-molecule resolution.

CO2 electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface

A very basic pathway from CO2 to ethylene Ethylene is an important commodity chemical for plastics. It is considered a tractable target for synthesizing renewably from carbon dioxide (CO2). The challenge is that the performance of the copper electrocatalysts used for this conversion under the required basic reaction conditions suffers from the competing reaction of CO2 with the base to form bicarbonate. Dinh et al. designed an electrode that tolerates the base by optimizing CO2 diffusion to the catalytic sites (see the Perspective by Ager and Lapkin). This catalyst design delivers 70% efficiency for 150 hours. Science, this issue p. 783; see also p. 707 Electrode design facilitates reductive coupling of CO2 to ethylene under otherwise inhibitory strongly basic conditions. Carbon dioxide (CO2) electroreduction could provide a useful source of ethylene, but low conversion efficiency, low production rates, and low catalyst stability limit current systems. Here we report that a copper electrocatalyst at an abrupt reaction interface in an alkaline electrolyte reduces CO2 to ethylene with 70% faradaic efficiency at a potential of −0.55 volts versus a reversible hydrogen electrode (RHE). Hydroxide ions on or near the copper surface lower the CO2 reduction and carbon monoxide (CO)–CO coupling activation energy barriers; as a result, onset of ethylene evolution at −0.165 volts versus an RHE in 10 molar potassium hydroxide occurs almost simultaneously with CO production. Operational stability was enhanced via the introduction of a polymer-based gas diffusion layer that sandwiches the reaction interface between separate hydrophobic and conductive supports, providing constant ethylene selectivity for an initial 150 operating hours.

Substrate-based platform for boosting the surface-enhanced Raman of plasmonic nanoparticles

Metal nanoparticles allow for surface-enhanced Raman scattering (SERS), with applications including spectroscopy and highly-multiplexed biolabels. Despite advances in nanoparticles design nanoparticles, the SERS from these systems is still weak when compared with randomly roughened substrates, and this limits their efficacy for many applications. Here, we coherently boost the SERS signal of colloidally-synthesized silver nano-prisms over 50 × by using multilayer substrates. Theoretical calculations verify the enhancement, and uncover the near-field response. This points the way toward a versatile platform for greater SERS enhancement from nanoparticles.

Metal nano-grid reflective wave plate

We propose an optical wave plate using a metal nano-grid. The wave plate operates in reflection mode. A single-mode truncated modematching theory is presented as a general method to design such nano-grid wave plates with the desired phase difference between the reflected TM and TE polarizations. This analytical theory allows angled incidence calculations as well, and numerical results agree-well with comprehensive finite-difference time-domain electromagnetic simulations. Due to the subwavelength path-length, the reflective wave plate is expected to have improved broad-band functionality over existing zero-order transmissive wave plates, for which an example is provided. The proposed wave plate is simple and compact, and it is amenable to existing nanofabrication techniques. The reflective geometry is especially promising for applications including liquid-crystal displays and laser feedback experiments.

Total optical transmission through a small hole in a metal waveguide screen.

We present the theory of total optical transmission through a small hole in metal waveguide screen. Unlike past works on extraordinary optical transmission using arrays, there is only a single hole; yet, the theory predicts total transmission for a perfect electric conductor (not normalized to the hole size) 100% transmission, regardless of how small the hole. This is very surprising considering the usual application of Bethes theory to waveguide apertures. Comprehensive numerical simulations agree well with the theory and their modal-analysis supports the proposed evanescent-mode mechanism for total transmission. These simulations are extended to show the influence of realistic material response (including loss) at microwave and visible-infrared frequencies. Due to the strong resonant field localization and transmission from only a thin metal screen with a single hole, many promising applications arise for this phenomenon including filtering, sensing, plasma generation, nonlinear optics, spectroscopy, heating, optical trapping, near-field microscopy and cavity quantum electrodynamics.