ZIF-Induced d-Band Modification in a Bimetallic Nanocatalyst: Achieving Over 44 % Efficiency in the Ambient Nitrogen Reduction Reaction.

The electrochemical nitrogen reduction reaction (NRR) offers a sustainable solution towards ammonia production but suffers poor reaction performance owing to preferential catalyst-H formation and the consequential hydrogen evolution reaction (HER). Now, the Pt/Au electrocatalyst d-band structure is electronically modified using zeolitic imidazole framework (ZIF) to achieve a Faradaic efficiency (FE) of >44 % with high ammonia yield rate of >161 µg mgcat -1 h-1 under ambient conditions. The strategy lowers electrocatalyst d-band position to weaken H adsorption and concurrently creates electron-deficient sites to kinetically drive NRR by promoting catalyst-N2 interaction. The ZIF coating on the electrocatalyst doubles as a hydrophobic layer to suppress HER, further improving FE by >44-fold compared to without ZIF (ca. 1 %). The Pt/Au-NZIF interaction is key to enable strong N2 adsorption over H atom.

Driving CO2 to a Quasi-Condensed Phase at the Interface between a Nanoparticle Surface and a Metal-Organic Framework at 1 bar and 298 K.

We demonstrate a molecular-level observation of driving CO2 molecules into a quasi-condensed phase on the solid surface of metal nanoparticles (NP) under ambient conditions of 1 bar and 298 K. This is achieved via a CO2 accumulation in the interface between a metal-organic framework (MOF) and a metal NP surface formed by coating NPs with a MOF. Using real-time surface-enhanced Raman scattering spectroscopy, a >18-fold enhancement of surface coverage of CO2 is observed at the interface. The high surface concentration leads CO2 molecules to be in close proximity with the probe molecules on the metal surface (4-methylbenzenethiol), and transforms CO2 molecules into a bent conformation without the formation of chemical bonds. Such linear-to-bent transition of CO2 is unprecedented at ambient conditions in the absence of chemical bond formation, and is commonly observed only in pressurized systems (>105 bar). The molecular-level observation of a quasi-condensed phase induced by MOF coating could impact the future design of hybrid materials in diverse applications, including catalytic CO2 conversion and ambient solid-gas operation.

Nanoporous Gold Bowls: A Kinetic Approach to Control Open Shell Structures and Size-Tunable Lattice Strain for Electrocatalytic Applications.

Controlling sub-10 nm ligament sizes and open-shell structure in nanoporous gold (NPG) to achieve strained lattice is critical in enhancing catalytic activity, but it remains a challenge due to poor control of reaction kinetics in conventional dealloying approach. Herein, a ligament size-controlled synthesis of open-shell NPG bowls (NPGB) through hetero-epitaxial growth of NPGB on AgCl is reported. The ligament size in NPGB is controlled from 6 to 46 nm by varying the hydroquinone to HAuCl4 ratio. The Williamson-Hall analysis demonstrates a higher lattice strain in smaller ligament size. In particular, NPGB with 6 nm (NPGB 6) ligament size possess the highest strain of 15.4 × 10(-3) , which is nearly twice of conventional 2D NPG sheets (≈8.8 × 10(-3) ). The presence of high surface energy facets in NPGBs is also envisaged. The best electrocatalytic activity toward methanol oxidation is observed in NPGB 6 (27.8 µA µg(-1) ), which is ≈9-fold and 3-fold higher than 8 nm solid Au nanoparticles, and conventional NPG sheets. The excellent catalytic activity in NPGB 6 is attributed to the open-shell structure, lattice strain, and higher electro-active surface area, allowing efficient exposure of catalytic active sites to facilitate the methanol oxidation. The results offer a potential strategy for designing next generation electrocatalysts.

Understanding the synthetic pathway of a single-phase quarternary semiconductor using surface-enhanced Raman scattering: a case of wurtzite Cu2ZnSnS4 nanoparticles.

Single-phase Cu2ZnSnS4 (CZTS) is an essential prerequisite toward a high-efficiency thin-film solar cell device. Herein, the selective phase formation of single-phase CZTS nanoparticles by ligand control is reported. Surface-enhanced Raman scattering (SERS) spectroscopy is demonstrated for the first time as a characterization tool for nanoparticles to differentiate the mixed compositional phase (e.g., CZTS, CTS, and ZnS), which cannot be distinguished by X-ray diffraction. Due to the superior selectivity and sensitivity of SERS, the growth mechanism of CZTS nanoparticle formation by hot injection is revealed to involve three growth steps. First, it starts with nucleation of Cu(2-x)S nanoparticles, followed by diffusion of Sn(4+) into Cu(2-x)S nanoparticles to form the Cu3SnS4 (CTS) phase and diffusion of Zn(2+) into CTS nanoparticles to form the CZTS phase. In addition, it is revealed that single-phase CZTS nanoparticles can be obtained via balancing the rate of CTS phase formation and diffusion of Zn(2+) into the CTS phase. We demonstrate that this balance can be achieved by 1 mL of thiol with Cu(OAc)2, Sn(OAc)4, and Zn(acac)2 metal salts to synthesize the CZTS phase without the presence of a detectable binary/ternary phase with SERS.

Precision synthesis: designing hot spots over hot spots via selective gold deposition on silver octahedra edges.

A major challenge in plasmonic hot spot fabrication is to efficiently increase the hot spot volumes on single metal nanoparticles to generate stronger signals in plasmon-enhanced applications. Here, the synthesis of designer nanoparticles, where plasmonic-active Au nanodots are selectively deposited onto the edge/tip hot spot regions of Ag nanoparticles, is demonstrated using a two-step seed-mediated precision synthesis approach. Such a "hot spots over hot spots" strategy leads to an efficient enhancement of the plasmonic hot spot volumes on single Ag nanoparticles. Through cathodoluminescence hyperspectral imaging of these selective edge gold-deposited Ag octahedron (SEGSO), the increase in the areas and emission intensities of hot spots on Ag octahedra are directly visualized after Au deposition. Single-particle surface-enhanced Raman scattering (SERS) measurements demonstrate 10-fold and 3-fold larger SERS enhancement factors of the SEGSO as compared to pure Ag octahedra and non-selective gold-deposited Ag octahedra (NSEGSO), respectively. The experimental results corroborate well with theoretical simulations, where the local electromagnetic field enhancement of our SEGSO particles is 15-fold and 1.3-fold stronger than pure Ag octahedra and facet-deposited particles, respectively. The growth mechanisms of such designer nanoparticles are also discussed together with a demonstration of the versatility of this synthetic protocol.

Roadmap on optical sensors.

Optical sensors and sensing technologies are playing a more and more important role in our modern world. From micro-probes to large devices used in such diverse areas like medical diagnosis, defence, monitoring of industrial and environmental conditions, optics can be used in a variety of ways to achieve compact, low cost, stand-off sensing with extreme sensitivity and selectivity. Actually, the challenges to the design and functioning of an optical sensor for a particular application requires intimate knowledge of the optical, material, and environmental properties that can affect its performance. This roadmap on optical sensors addresses different technologies and application areas. It is constituted by twelve contributions authored by world-leading experts, providing insight into the current state-of-the-art and the challenges their respective fields face. Two articles address the area of optical fibre sensors, encompassing both conventional and specialty optical fibres. Several other articles are dedicated to laser-based sensors, micro- and nano-engineered sensors, whispering-gallery mode and plasmonic sensors. The use of optical sensors in chemical, biological and biomedical areas is discussed in some other papers. Different approaches required to satisfy applications at visible, infrared and THz spectral regions are also discussed.

Bimetallic platonic Janus nanocrystals.

We demonstrate the creation of Ag-based bimetallic platonic Janus nanostructures by confining galvanic replacement reaction at a nanoscale interface on highly symmetrical nanostructures such as Ag nanocubes and nanooctahedra using reactive microcontact printing (µCP). The extent of galvanic replacement reaction can be controlled kinetically to derive Janus nanostructures with Au nanodots deposited on either one or multiple facets of Ag nanocubes. The selective deposition of Au dots on a single facet of Ag nanocubes breaks the cubic symmetry and brings about unique and anisotropic plasmonic responses. High-resolution cathodoluminescence hyperspectral imaging of single Janus nanocube demonstrates that surface plasmon resonances corresponding to Au and Ag can be excited at different spots on one Janus nanocube. In addition, we demonstrate the fabrication of alternating Janus/non-Janus segments on 2D Ag nanowires by using a line-patterned polydimethylsiloxane (PDMS) stamp for galvanic replacement. Aside from Au, Pt and Pd can also be selectively deposited onto Ag nanocubes. These Janus nanostructures may find important applications in the field of plasmon-enhanced catalysis.

A chemical route to increase hot spots on silver nanowires for surface-enhanced Raman spectroscopy application.

The effective number of surface-enhanced Raman spectroscopy (SERS) active hot spots on plasmonic nanostructures is the most crucial factor in ensuring high sensitivity in SERS sensing platform. Here we demonstrate a chemical etching method to increase the surface roughness of one-dimensional Ag nanowires, targeted at creating more SERS active hot spots along Ag nanowire's longitudinal axis for increased SERS detection sensitivity. Silver nanowires were first synthesized by the conventional polyol method and then subjected to chemical etching by NH(4)OH and H(2)O(2) mixture. The surfaces of silver nanowires were anisotropically etched off to create miniature "beads on a string" features with increased surface roughness while their crystallinity was preserved. Mapping of single-nanowire SERS measurements showed that the chemical etching method has overcome the limitation of conventional one-dimensional Ag nanowires with limited SERS active area at the tips to produce etched Ag nanowires with an increase in Raman hot spots and polarization-independent SERS signals across tens of micrometers length scale.

Graphene oxide and shape-controlled silver nanoparticle hybrids for ultrasensitive single-particle surface-enhanced Raman scattering (SERS) sensing.

Graphene oxide (GO) is an emerging material for surface-enhanced Raman scattering (SERS) due to its strong chemical enhancement. Studying the SERS performance of plasmonic nanoparticle/GO hybrid materials at the single particle level is crucial for direct probing of the chemical effect of GO on plasmonic nanoparticles. In this work, we integrate GO and shape-controlled Ag nanoparticles to create hybrid nanomaterials, and the chemical enhancement arising from GO is investigated using single-particle SERS measurements. Ag nanoparticle@GO hybrid nanostructures are prepared by assembling Ag nanoparticles, including spheres, cubes and octahedra with GO sheets. The SERS behaviors of the hybrid nanostructures are characterized, and 2-3 times enhanced SERS intensities are detected from the Ag nanoparticle@GO hybrid nanostructures as compared to pure Ag nanoparticles. Furthermore, we probe the mechanism of SERS enhancement in the hybrid nanostructures by changing the surface coverage of GO on Ag octahedra, by using reduced GO in place of GO as well as by using probe molecules of different electronegativities. This hybrid system is an excellent candidate for single-particle SERS sensors. Sub-nanomolar levels of aromatic molecules are detected using a single Ag/GO hybrid nanomaterial. This as-prepared GO and shape-controlled Ag nanoparticle hybrid is capable of serving as a high performance SERS platform, providing new opportunities for efficient chemical and biological sensing applications.

One-step synthesis of zero-dimensional hollow nanoporous gold nanoparticles with enhanced methanol electrooxidation performance.

Nanoporous gold with networks of interconnected ligaments and highly porous structure holds stimulating technological implications in fuel cell catalysis. Current syntheses of nanoporous gold mainly revolve around de-alloying approaches that are generally limited by stringent and harsh multistep protocols. Here we develop a one-step solution phase synthesis of zero-dimensional hollow nanoporous gold nanoparticles with tunable particle size (150-1,000 nm) and ligament thickness (21-54 nm). With faster mass diffusivity, excellent specific electroactive surface area and large density of highly active surface sites, our zero-dimensional nanoporous gold nanoparticles exhibit ~1.4 times enhanced catalytic activity and improved tolerance towards carbonaceous species, demonstrating their superiority over conventional nanoporous gold sheets. Detailed mechanistic study also reveals the crucial heteroepitaxial growth of gold on the surface of silver chloride templates, implying that our synthetic protocol is generic and may be extended to the synthesis of other nanoporous metals via different templates.