High index contrast photonic platforms for on-chip Raman spectroscopy

Nanophotonic waveguide enhanced Raman spectroscopy (NWERS) is a sensing technique that uses a highly confined waveguide mode to excite and collect the Raman scattered signal from molecules in close vicinity of the waveguide. The most important parameters defining the figure of merit of an NWERS sensor include its ability to collect the Raman signal from an analyte, i.e. "the Raman conversion efficiency" and the amount of "Raman background" generated from the guiding material. Here, we compare different photonic integrated circuit (PIC) platforms capable of on-chip Raman sensing in terms of the aforementioned parameters. Among the four photonic platforms under study, tantalum oxide and silicon nitride waveguides exhibit high signal collection efficiency and low Raman background. In contrast, the performance of titania and alumina waveguides suffers from a strong Raman background and a weak signal collection efficiency, respectively

Unusual synergistic effect in layered Ruddlesden-Popper oxide enables ultrafast hydrogen evolution

Efficient electrocatalysts for hydrogen evolution reaction are key to realize clean hydrogen production through water splitting. As an important family of functional materials, transition metal oxides are generally believed inactive towards hydrogen evolution reaction, although many of them show high activity for oxygen evolution reaction. Here we report the remarkable electrocatalytic activity for hydrogen evolution reaction of a layered metal oxide, Ruddlesden-Popper-type Sr2RuO4 with alternative perovskite layer and rock-salt SrO layer, in an alkaline solution, which is comparable to those of the best electrocatalysts ever reported. By theoretical calculations, such excellent activity is attributed mainly to an unusual synergistic effect in the layered structure, whereby the (001) SrO-terminated surface cleaved in rock-salt layer facilitates a barrier-free water dissociation while the active apical oxygen site in perovskite layer promotes favorable hydrogen adsorption and evolution. Moreover, the activity of such layered oxide can be further improved by electrochemistry-induced activation

Strongly Coupled Magnetic and Electronic Transitions in Multivalent Strontium Cobaltites

The topotactic phase transition in SrCoOx (x = 2.5-3.0) makes it possible to reversibly transit between the two distinct phases, i.e. the brownmillerite SrCoO2.5 that is a room-temperature antiferromagnetic insulator (AFM-I) and the perovskite SrCoO3 that is a ferromagnetic metal (FM-M), owing to their multiple valence states. For the intermediate x values, the two distinct phases are expected to strongly compete with each other. With oxidation of SrCoO2.5, however, it has been conjectured that the magnetic transition is decoupled to the electronic phase transition, i.e., the AFM-to-FM transition occurs before the insulator-to-metal transition (IMT), which is still controversial. Here, we bridge the gap between the two-phase transitions by density-functional theory calculations combined with optical spectroscopy. We confirm that the IMT actually occurs concomitantly with the FM transition near the oxygen content x = 2.75. Strong charge-spin coupling drives the concurrent IMT and AFM-to-FM transition, which fosters the near room-T magnetic transition characteristic. Ultimately, our study demonstrates that SrCoOx is an intriguingly rare candidate for inducing coupled magnetic and electronic transition via fast and reversible redox reactions

Bifunctional non-noble metal oxide nanoparticle electrocatalysts through lithium-induced conversion for overall water splitting

Developing earth-abundant, active and stable electrocatalysts which operate in the same electrolyte for water splitting, including oxygen evolution reaction and hydrogen evolution reaction, is important for many renewable energy conversion processes. Here we demonstrate the improvement of catalytic activity when transition metal oxide (iron, cobalt, nickel oxides and their mixed oxides) nanoparticles (~20 nm) are electrochemically transformed into ultra-small diameter (2–5 nm) nanoparticles through lithium-induced conversion reactions. Different from most traditional chemical syntheses, this method maintains excellent electrical interconnection among nanoparticles and results in large surface areas and many catalytically active sites. We demonstrate that lithium-induced ultra-small NiFeOx nanoparticles are active bifunctional catalysts exhibiting high activity and stability for overall water splitting in base. We achieve 10 mA cm−2 water-splitting current at only 1.51 V for over 200 h without degradation in a two-electrode configuration and 1 M KOH, better than the combination of iridium and platinum as benchmark catalysts.open10

Promotion of oxygen reduction by a bio-inspired tethered iron phthalocyanine carbon nanotube-based catalyst

Electrocatalysts for oxygen reduction are a critical component that may dramatically enhance the performance of fuel cells and metal-air batteries, which may provide the power for future electric vehicles. Here we report a novel bio-inspired composite electrocatalyst, iron phthalocyanine with an axial ligand anchored on single-walled carbon nanotubes, demonstrating higher electrocatalytic activity for oxygen reduction than the state-of-the-art Pt/C catalyst as well as exceptional durability during cycling in alkaline media. Theoretical calculations suggest that the rehybridization of Fe 3d orbitals with the ligand orbitals coordinated from the axial direction results in a significant change in electronic and geometric structure, which greatly increases the rate of oxygen reduction reaction. Our results demonstrate a new strategy to rationally design inexpensive and durable electrochemical oxygen reduction catalysts for metal-air batteries and fuel cells.close34

Seed-mediated atomic-scale reconstruction of silver manganate nanoplates for oxygen reduction towards high-energy aluminum-air flow batteries

Aluminum-air batteries are promising candidates for next-generation high-energy-density storage, but the inherent limitations hinder their practical use. Here, we show that silver nanoparticle-mediated silver manganate nanoplates are a highly active and chemically stable catalyst for oxygen reduction in alkaline media. By means of atomic-resolved transmission electron microscopy, we find that the formation of stripe patterns on the surface of a silver manganate nanoplate originates from the zigzag atomic arrangement of silver and manganese, creating a high concentration of dislocations in the crystal lattice. This structure can provide high electrical conductivity with low electrode resistance and abundant active sites for ion adsorption. The catalyst exhibits outstanding performance in a flow-based aluminum-air battery, demonstrating high gravimetric and volumetric energy densities of similar to 2552 Wh kg(Al)(-1) and similar to 6890 Wh I-Al(-1) at 100 mA cm(-2), as well as high stability during a mechanical recharging process

Self-optimizing, highly surface-active layered metal dichalcogenide catalysts for hydrogen evolution

Low-cost, layered transition-metal dichalcogenides (MX_2) based on molybdenum and tungsten have attracted substantial interest as alternative catalysts for the hydrogen evolution reaction (HER). These materials have high intrinsic per-site HER activity; however, a significant challenge is the limited density of active sites, which are concentrated at the layer edges. Here we unravel electronic factors underlying catalytic activity on MX_2 surfaces, and leverage the understanding to report group-5 MX_2 (H-TaS_2 and H-NbS_2) electrocatalysts whose performance instead mainly derives from highly active basal-plane sites, as suggested by our first-principles calculations and performance comparisons with edge-active counterparts. Beyond high catalytic activity, they are found to exhibit an unusual ability to optimize their morphology for enhanced charge transfer and accessibility of active sites as the HER proceeds, offering a practical advantage for scalable processing. The catalysts reach 10 mA cm^(−2) current density at an overpotential of ∼50–60 mV with a loading of 10–55 μg cm^(−2), surpassing other reported MX2 candidates without any performance-enhancing additives

Atomically dispersed nickel-nitrogen-sulfur species anchored on porous carbon nanosheets for efficient water oxidation

Developing low-cost electrocatalysts to replace precious Ir-based materials is key for oxygen evolution reaction (OER). Here, we report atomically dispersed nickel coordinated with nitrogen and sulfur species in porous carbon nanosheets as an electrocatalyst exhibiting excellent activity and durability for OER with a low overpotential of 1.51 V at 10 mA cm(-2) and a small Tafel slope of 45 mV dec(-1) in alkaline media. Such electrocatalyst represents the best among all reported transition metal- and/or heteroatom-doped carbon electrocatalysts and is even superior to benchmark Ir/C. Theoretical and experimental results demonstrate that the well-dispersed molecular S vertical bar NiNx species act as active sites for catalyzing OER. The atomic structure of S vertical bar NiNx centers in the carbon matrix is clearly disclosed by aberration-corrected scanning transmission electron microscopy and synchrotron radiation X-ray absorption spectroscopy together with computational simulations. An integrated photoanode of nanocarbon on a Fe2O3 nanosheet array enables highly active solar-driven oxygen production

Mesoporous Ternary Nitrides of Earth-Abundant Metals as Oxygen Evolution Electrocatalyst

As sustainable energy becomes a major concern for modern society, renewable and clean energy systems need highly active, stable, and low-cost catalysts for the oxygen evolution reaction (OER). Mesoporous materials offer an attractive route for generating efficient electrocatalysts with high mass transport capabilities. Herein, we report an efficient hard templating pathway to design and synthesize three-dimensional (3-D) mesoporous ternary nickel iron nitride (Ni3FeN). The as-synthesized electrocatalyst shows good OER performance in an alkaline solution with low overpotential (259 mV) and a small Tafel slope (54 mV dec(−1)), giving superior performance to IrO(2) and RuO(2) catalysts. The highly active contact area, the hierarchical porosity, and the synergistic effect of bimetal atoms contributed to the improved electrocatalytic performance toward OER. In a practical rechargeable Zn–air battery, mesoporous Ni(3)FeN is also shown to deliver a lower charging voltage and longer lifetime than RuO(2). This work opens up a new promising approach to synthesize active OER electrocatalysts for energy-related devices. [Image: see text] ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (10.1007/s40820-020-0412-8) contains supplementary material, which is available to authorized users