Low-loss tantalum pentoxide photonics with a CMOS-compatible process.

We report a Ta2O5 photonic platform with a propagation loss of 0.49 dB/cm at 1550 nm, of 0.86 dB/cm at 780 nm, and of 3.76 dB/cm at 2000 nm. The thermal bistability measurement is conducted in the entire C-band for the first time to reveal the absorption loss of Ta2O5 waveguides, offering guidelines for further reduction of the waveguide loss. We also characterize the Ta2O5 waveguide temperature response, which shows favorable thermal stability. The fabrication process temperature is below 350°C, which is friendly to integration with active optoelectronic components.

Monitoring surface dynamics of electrodes during electrocatalysis using in situ synchrotron FTIR spectroscopy.

Monitoring the surface dynamics of catalysts under working conditions is important for a deep understanding of the underlying electrochemical mechanisms towards efficient energy conversion and storage. Fourier transform infrared (FTIR) spectroscopy with high surface sensitivity has been considered as a powerful tool for detecting surface adsorbates, but it faces a great challenge when being adopted in surface dynamics investigations during electrocatalysis due to the complication and influence of aqueous environments. This work reports a well designed FTIR cell with tunable micrometre-scale water film over the surface of working electrodes and dual electrolyte/gas channels for in situ synchrotron FTIR tests. By coupling with a facile single-reflection infrared mode, a general in situ synchrotron radiation FTIR (SR-FTIR) spectroscopic method is developed for tracking the surface dynamics of catalysts during the electrocatalytic process. As an example, in situ formed key *OOH is clearly observed on the surface of commercial benchmark IrO2 catalysts during the electrochemical oxygen evolution process based on the developed in situ SR-FTIR spectroscopic method, which demonstrates its universality and feasibility in surface dynamics studies of electrocatalysts under working conditions.

Tracking the Oxygen Dynamics of Solid-Liquid Electrochemical Interfaces by Correlative In Situ Synchrotron Spectroscopies.

Oxygen-involved electrocatalytic processes, including the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), are central to a series of advanced modern energy and conversion technologies, such as water electrolyzers, fuel cells, and CO2 reduction or N2 fixation devices. A comprehensive and in-depth understanding of the charge transfer and energy conversion process that ubiquitously occurs over solid-liquid electrochemical interfaces during oxygen electrocatalysis is crucial for understanding the key essence of oxygen-related electrochemistry. The huge challenges for dynamic studies over solid-liquid interfaces during oxygen electrocatalysis lie in the all-embracing electrochemical processes of the catalytic reactions, associated with both structural and reactive intermediates evolution on the electrode surface, and in the significant influence of the aqueous environments of electrolytes used. Hence, overcoming these challenges intrinsically calls for a great cooperation of multiple cutting-edge in situ technologies. Synchrotron radiation (SR) X-ray absorption fine structure (SR-XAFS) spectroscopy is highly sensitive to the local atomic structure of nanomaterials, and SR-based Fourier transform infrared (SR-FTIR) spectroscopy features unique molecular fingerprint identification to determine active species on the surface of electrodes. One can imagine that the correlative in situ SR-XAFS/FTIR spectroscopic investigations will potentially provide sufficient, reliable, and complementary information at the atomic/molecular level to depict vivid and comprehensive "dynamic movies" of solid-liquid electrochemical interfaces during oxygen electrocatalysis, which will help effectively promote/simplify the complicated screening process of advanced oxygen electrocatalysts for efficient high-energy-density energy systems.In this Account, starting with some fundamentals of SR-based spectroscopic technologies, tips for obtaining high-quality SR-XAFS and SR-FTIR spectroscopy results during the electrocatalytic process are comprehensively specified. Subsequently, the latest research achievements of dynamic investigations mainly from our group based on in situ SR-XAFS and/or SR-FTIR spectroscopies will be systematically scrutinized and properly emphasized in detail, where the currently attractive metal-organic-framework (MOF) nanomaterials and single-atom catalysts (SACs) are selected as the main object of research. Moreover, the vital contributions of correlative in situ SR-XAFS/FTIR studies on new discoveries of the dynamic evolution of solid-liquid interfaces during oxygen electrocatalysis are highlighted. In particular, our pioneering research found that the potential-dependent dynamically coupled oxygen formed in the precatalytic stage was a very useful promoter in SACs to promote efficient OER kinetics under acidic conditions. In addition, the in situ generated metastable Ni1-N2 centers with more structural degrees of freedom in SACs could potentially facilitate the fast 4e- ORR kinetics. This Account is anticipated to stimulate broad interest in dynamic explorations in various catalytic processes of interest in the material science and electrochemistry communities using correlative SR-based technologies.

Wafer-scale inverted gallium phosphide-on-insulator rib waveguides for nonlinear photonics.

We report a gallium phosphide-on-insulator (GaP-OI) photonic platform fabricated by an intermediate-layer bonding process aiming to increase the manufacture scalability in a low-cost manner. This is enabled by the "etch-n-transfer" sequence, which results in inverted rib waveguide structures. The shallow-etched 1.8 µm-wide waveguide has a propagation loss of 23.5 dB/cm at 1550 nm wavelength. Supercontinuum generation based on the self-phase modulation effect is observed when the waveguides are pumped by femtosecond pulses. The nonlinear refractive index of GaP, n2, is extracted to be 1.9 × 10-17 m2/W, demonstrating the great promise of the GaP-OI platform in third-order nonlinear applications.

Synergetic Dual-Ion Centers Boosting Metal Organic Framework Alloy Catalysts toward Efficient Two Electron Oxygen Reduction.

Herein, a strategy of synergetic dual-metal-ion centers to boost transition-metal-based metal organic framework (MOF) alloy nanomaterials as active oxygen reduction reaction (ORR) electrocatalysts for efficient hydrogen peroxide (H2 O2 ) generation is proposed. Through a facile one-pot wet chemical method, a series of MOF alloys with unique Ni-M (M-Co, Cu, Zn) synergetic centers are synthesized, where the strong metallic ions 3d-3d synergy can effectively inhibit O2 cleavage on Ni sites toward a favorable two-electron ORR pathway. Impressively, the well-designed NiZn MOF alloy catalysts show an excellent H2 O2 selectivity up to 90% during ORR, evidently outperforming that of NiCo MOF (45%), and NiCu MOF (55%). Moreover, it sustains efficient activity and robust stability under a continuous longterm ORR operation. The correlative in situ synchrotron radiation X-ray adsorption fine structure and Fourier transform infrared spectroscopy analyses reveal at the atomic level that, the higher Ni oxidation states species, regulated via adjacent Zn2+ ions, are favorable for optimizing the adsorption energetics of key *OOH intermediates toward fast two electron ORR kinetics.

Atomically Dispersed Reactive Centers for Electrocatalytic CO2 Reduction and Water Splitting.

Developing electrocatalytic energy conversion technologies for replacing the traditional energy source is highly expected to resolve the fossil fuel exhaustion and related environmental problems. Exploring stable and high-efficiency electrocatalysts is of vital importance for the promotion of these technologies. Single-atom catalysts (SACs), with atomically distributed active sites on supports, perform as emerging materials in catalysis and present promising prospects for a wide range of applications. The rationally designed near-range coordination environment, long-range electronic interaction and microenvironment of the coordination sphere cast huge influence on the reaction mechanism and related catalytic performance of SACs. In the current Review, some recent developments of atomically dispersed reactive centers for electrocatalytic CO2 reduction and water splitting are well summarized. The catalytic mechanism and the underlying structure-activity relationship are elaborated based on the recent progresses of various operando investigations. Finally, by highlighting the challenges and prospects for the development of single-atom catalysis, we hope to shed some light on the future research of SACs for the electrocatalytic energy conversion.

Synergetic Cobalt-Copper-Based Bimetal-Organic Framework Nanoboxes toward Efficient Electrochemical Oxygen Evolution.

The development of efficient oxygen electrocatalysts and understanding their underlying catalytic mechanism are of significant importance for the high-performance energy conversion and storage technologies. Herein, we report novel CoCu-based bimetallic metal-organic framework nanoboxes (CoCu-MOF NBs) as promising catalysts toward efficient electrochemical oxygen evolution reaction (OER), fabricated via a successive cation and ligand exchange strategy. With the highly exposed bimetal centers and the well-designed architecture, the CoCu-MOF NBs show excellent OER activity and stability, with a small overpotential of 271 mV at 10 mA cm-2 and a high turnover frequency value of 0.326 s-1 at an overpotential of 300 mV. In combination of quasi in situ X-ray absorption fine structure spectroscopy and density-functional theory calculations, the post-formed CoCu-based oxyhydroxide analogue during OER is believed to account for the high OER activity of CoCu-MOF NBs, where the electronic synergy between Co and neighbouring Cu atoms promotes the O-O bond coupling toward fast OER kinetics.

Dynamic Evolution of Solid-Liquid Electrochemical Interfaces over Single-Atom Active Sites.

The structural dynamics of the solid-liquid interfaces (SLEIs) determines the chemistry in all electrochemical processes. Here, by combining multiple operando synchrotron spectroscopies, we identify at the atomic level a general evolution of single-atom Ni at SLEIs into a near-free atom state in the electrochemical oxygen reduction reaction (ORR). We uncover that the single-atom Ni at SLEIs tends to be dynamically released from the nitrogen-carbon substrate and then forms a near-free, isolated-zigzag active site (Ni1(2-δ)+N2) during the reaction. This isolated-zigzag Ni1(2-δ)+N2 active site facilitates the adsorption and dissociation of O2 into a crucial *O intermediate within the electrical double layers, realizing a highly efficient single-atom catalyst with the best ORR performance in alkaline solutions reported thus far. These findings may pave a general way for dissecting other important structural dynamic processes at SLEIs, such as hydrogen evolution, oxygen evolution, and CO2 reduction reactions.

NiMn-Based Bimetal-Organic Framework Nanosheets Supported on Multi-Channel Carbon Fibers for Efficient Oxygen Electrocatalysis.

Developing noble-metal-free bifunctional oxygen electrocatalysts is of great significance for energy conversion and storage systems. Herein, we have developed a transformation method for growing NiMn-based bimetal-organic framework (NiMn-MOF) nanosheets on multi-channel carbon fibers (MCCF) as a bifunctional oxygen electrocatalyst. Owing to the desired components and architecture, the MCCF/NiMn-MOFs manifest comparable electrocatalytic performance towards oxygen reduction reaction (ORR) with the commercial Pt/C electrocatalyst and superior performance towards oxygen evolution reaction (OER) to the benchmark RuO2 electrocatalyst. X-ray absorption fine structure (XAFS) spectroscopy and density functional theory (DFT) calculations reveal that the strong synergetic effect of adjacent Ni and Mn nodes within MCCF/NiMn-MOFs effectively promotes the thermodynamic formation of key *O and *OOH intermediates over active NiO6 centers towards fast ORR and OER kinetics.

Potential-driven surface active structure rearrangement over FeP@NC towards efficient electrocatalytic hydrogen evolution.

Understanding the variation of active structure during the hydrogen evolution reaction (HER) process is of great importance for aiding in the design of optimized electrocatalysts. Herein, we present a composite material of FeP nanoparticles coated by N-doped carbon (FeP@NC) as an efficient HER electrocatalyst, synthesized by a pyrolysis and equivalent-volume impregnation method. The as-prepared FeP@NC catalyst can accelerate the HER at a small overpotential of 135 mV with a current density of 10 mA cm-2 in acidic medium and also shows a robust long-term stability with a minor decay of about 10% of the initial current density after 15 h. Using in situ X-ray absorption spectroscopy (XAS), a potential-dependent surface rearrangement of a surface pentahedral Fe structure into an octahedral Fe moiety via surface hydroxylation is clearly observed during the HER process, resulting in a much higher electrocatalytic activity. The theoretical calculations further unveil that the rearrangement of the surface FeP5(OH) octahedral structure could effectively trigger the adjacent P atoms to act as favorable proton acceptor sites towards improving the reaction kinetics of the Volmer step for efficient electrochemical hydrogen evolution.

Fast Photoelectron Transfer in (Cring)-C3N4 Plane Heterostructural Nanosheets for Overall Water Splitting.

Direct and efficient photocatalytic water splitting is critical for sustainable conversion and storage of renewable solar energy. Here, we propose a conceptual design of two-dimensional C3N4-based in-plane heterostructure to achieve fast spatial transfer of photoexcited electrons for realizing highly efficient and spontaneous overall water splitting. This unique plane heterostructural carbon ring (Cring)-C3N4 nanosheet can synchronously expedite electron-hole pair separation and promote photoelectron transport through the local in-plane π-conjugated electric field, synergistically elongating the photocarrier diffusion length and lifetime by 10 times relative to those achieved with pristine g-C3N4. As a result, the in-plane (Cring)-C3N4 heterostructure could efficiently split pure water under light irradiation with prominent H2 production rate up to 371 µmol g-1 h-1 and a notable quantum yield of 5% at 420 nm.

Highly Active Graphene Oxide-Supported Cobalt Single-Ion Catalyst for Chemiluminescence Reaction.

Graphene- or graphene oxide (GO)-supported metallic nanoparticles and single metal atom as potentially effective catalysts for chemical reactions have recently received extensive research interests. However, metal utilization in nanoparticle catalysts is limited and metal atoms readily drift on the graphene surface and consequently form aggregated large particles, making practical applications limited. Here, we report metal ions directly immobilized on GO as a novel GO-supported single-ion catalyst for chemiluminecence (CL) reactions. It is found that GO-supported cobalt ions with good stability could catalyze strongly luminol-H2O2 and lucigenin-H2O2 CL reactions, accompanied by dramatically enhanced CL emission. Theoretical studies reveal that the coupling between Co2+ and GO induces effective polarization charges, improving chemical activity of the reaction site, which promotes the generation of intermediate radicals and accelerates the CL reactions. This work may be generalized to other GO-supported metal ions as catalysts for a wide range of chemical reactions. The developed GO-supported cobalt single-ion nanocomposites as nanointerfaces may find future applications in CL bioassays.

Single-Site Active Cobalt-Based Photocatalyst with a Long Carrier Lifetime for Spontaneous Overall Water Splitting.

An active and stable photocatalyst to directly split water is desirable for solar-energy conversion. However, it is difficult to accomplish overall water splitting without sacrificial electron donors. Herein, we demonstrate a strategy via constructing a single site to simultaneously promote charge separation and catalytic activity for robust overall water splitting. A single Co1 -P4 site confined on g-C3 N4 nanosheets was prepared by a facile phosphidation method, and identified by electron microscopy and X-ray absorption spectroscopy. This coordinatively unsaturated Co site can effectively suppress charge recombination and prolong carrier lifetime by about 20 times relative to pristine g-C3 N4 , and boost water molecular adsorption and activation for oxygen evolution. This single-site photocatalyst exhibits steady and high water splitting activity with H2 evolution rate up to 410.3 µmol h-1 g-1 , and quantum efficiency as high as 2.2 % at 500 nm.

Michael Addition Polymerization of Trifunctional Amine and Acrylic Monomer: A Versatile Platform for Development of Biomaterials.

Michael addition polymerizations of amines and acrylic monomers are versatile approaches to biomaterials for various applications. A combinatorial library of poly(ß-amino ester)s and diverse poly(amido amine)s from diamines and diacrylates or bis(acrylamide)s have been reported, respectively. Furthermore, novel linear and hyperbranched polymers from Michael addition polymerizations of trifunctional amines and acrylic monomers significantly enrich this category of biomaterials. In this Review, we focus on the biomaterials from Michael addition polymerizations of trifunctional amines and acrylic monomers. First we discuss how the polymerization mechanisms, which are determined by the reactivity sequence of the three types of amines of trifunctional amines, i.e., secondary (2°) amines (original), primary (1°) amines, and 2° amines (formed), are affected by the chemistry of monomers, reaction temperature, and solvent. Then we update how to design and synthesize linear and hyperbranched polymers based on the understanding of polymerization mechanisms. Linear polymers containing 2° amines in the backbones can be obtained from polymerizations of diacrylates or bis(acrylamide)s with equimolar trifunctional amine, and several approaches, e.g., 2A2+BB'B″, A3+2BB'B', A2+BB'B″, to hyperbranched polymers are developed. Further through molecular design of monomers, conjugation of functional species to 2° amines in the backbones of linear polymers and the abundant terminal groups of hyperbranched polymers, the amphiphilicity of polymers can be adjusted, and additional stimuli, e.g., thermal, redox, reactive oxidation species (ROS), and light, responses can be integrated with the intrinsic pH response. Finally we discuss the applications of the polymers for gene/drug delivery and bioimaging through exploring their self-assemblies in various motifs, e.g., micelles, polyplexes particles/nanorings and hydrogels. Redox-responsive hyperbranched polymers can display 300 times higher in vitro gene transfection efficiency and provide a higher in vivo siRNA efficacy than PEI. Also redox-responsive micelle carriers can improve the efficacy of anticancer drug and the bioimaging contrast. Further molecular design and optimization of this category of polymers together with in vivo studies should provide safe and efficient biomaterials for clinical applications.

Surfactant-Free Emulsion-Based Preparation of Redox-Responsive Nanogels.

A surfactant-free emulsion-based approach is developed for preparation of nanogels. A water-in-oil emulsion is generated feasibly from a mixture of water and a solution of disulfide-containing hyperbranched PEGylated poly(amido amine)s, poly(BAC2-AMPD1)-PEG, in chloroform. The water droplets in the emulsion are stabilized and filled with poly(BAC2-AMPD1)-PEG, and the crosslinked poly(amido amine)s nanogels are formed via the intermolecular disulfide exchange reaction. FITC-dextran is loaded within the nanogels by dissolving the compound in water before emulsification. Transmission electron microscopy and dynamic light scattering are applied to characterize the emulsion and the nanogels. The effects of the homogenization rate and the ratio of water/polymer are investigated. Redox-induced degradation and FITC-dextran release profile of the nanogels are monitored, and the results show efficient loading and redox-responsive release of FITC-dextran. This is a promising approach for the preparation of nanogels for drug delivery, especially for neutral charged carbohydrate-based drugs.

CoOOH Nanosheets with High Mass Activity for Water Oxidation.

Endowing transition-metal oxide electrocatalysts with high water oxidation activity is greatly desired for production of clean and sustainable chemical fuels. Here, we present an atomically thin cobalt oxyhydroxide (γ-CoOOH) nanosheet as an efficient electrocatalyst for water oxidation. The 1.4 nm thick γ-CoOOH nanosheet electrocatalyst can effectively oxidize water with extraordinarily large mass activities of 66.6 A g(-1), 20 times higher than that of γ-CoOOH bulk and 2.4 times higher than that of the benchmarking IrO2 electrocatalyst. Experimental characterizations and first-principles calculations provide solid evidence to the half-metallic nature of the as-prepared nanosheets with local structure distortion of the surface CoO(6-x) octahedron. This greatly enhances the electrophilicity of H2O and facilitates the interfacial electron transfer between Co ions and adsorbed -OOH species to form O2, resulting in the high electrocatalytic activity of layered CoOOH for water oxidation.

Half-unit-cell α-Fe2O3 semiconductor nanosheets with intrinsic and robust ferromagnetism.

The synthesis of atomically thin transition-metal oxide nanosheets as a conceptually new class of materials is significant for the development of next-generation electronic and magnetic nanodevices but remains a fundamental chemical and physical challenge. Here, based on a "template-assisted oriented growth" strategy, we successfully synthesized half-unit-cell nanosheets of a typical transition-metal oxide α-Fe2O3 that show robust intrinsic ferromagnetism of 0.6 µB/atom at 100 K and remain ferromagnetic at room temperature. A unique surface structure distortion, as revealed by X-ray absorption spectroscopy, produces nonidentical Fe ion environments and induces distance fluctuation of Fe ion chains. First-principles calculations reveal that the efficient breaking of the quantum degeneracy of Fe 3d energy states activates ferromagnetic exchange interaction in these Fe(5-co)-O-Fe(6-co) ion chains. These results provide a solid design principle for tailoring the spin-exchange interactions and offer promise for future semiconductor spintronics.

Fluorescent carbon dot (C-dot) nanoclusters.

Fluorescent carbon dot (C-dot) nanoclusters composed of C-dot-loaded hollow silica spheres are obtained via the dehydration of mannose, which is adsorbed onto hollow silica spheres or poly(ethylene glycol)-graft-hollow silica spheres (PEG-g-hollow silica). The structure of C-dot nanoclusters are confirmed using 1H NMR, FTIR, TEM and TGA. C-dot nanoclusters show a redshifted fluorescence emission with an increased excitation wavelength. Passivation with PEG diamines improve the quantum yields to ∼2%. Confocal laser scanning microscopy (CLSM) results reflect the fact that C-dot nanoclusters can provide good cytoplasm imaging of live Hep G2 cells and live MCF-7 cells, and the imaging obtained is brighter and more even than those from free C-dots. With their combination of good photostability and low cytotoxicity, C-dot nanoclusters are promising for the production of higher quality bioimaging.

Engineering High-Spin State Cobalt Cations in Sulfide Spinel for Enhancing Water Oxidation.

The spin states of active sites have a significant impact on the adsorption/desorption ability of the reaction intermediates during the oxygen evolution reaction (OER). Sulfide spinel is not generally considered a highly efficient OER catalyst owing to the low spin state of Co3+ and the lack of unpaired electrons available for adsorption of reaction intermediates. Herein, it is proposed a novel Nd-evoked valence electronic adjustment strategy to engineer the spin state of Co ions. The unique f-p-d orbital electronic coupling effect stimulates the rearrangement of Co d orbital electrons and increases the eg electron filling to achieve high-spin state Co ions, which promotes charge transport by propagating a spin channel and generates a high number of active sites for intermediate adsorption. The optimized CuCo1.75 Nd0.25 S4 catalyst exhibits outstanding electrocatalytic properties with a low overpotential of 320 mV at 500 mA cm-2 and a 48 h stability at 300 mA cm-2 . In situ synchrotron radiation infrared spectra confirm the quick accumulation of key *OOH and *O intermediates. This work deepens the comprehensive understanding of the relationship between OER activity and spin configurations of Co ions and offers a new design strategy for spinel compound catalysts.

Redox-responsive hyperbranched poly(amido amine)s with tertiary amino cores for gene delivery.

Redox-responsive hyperbranched poly(amido amine)s (PAAs) with tertiary amino cores and amine, poly(ethylene glycol) (PEG) and hydroxyl terminal groups were prepared for DNA delivery respectively. The DNA condensation capability of PAAs was investigated using gel electrophoresis, and the results showed that PAA terminated with 1-(2-aminoethyl)piperazine (AEPZ) (BAA) is the most efficient in binding plasmid DNA (pDNA). The diameter and zeta-potential of polyplexes from PAAs were characterized using dynamic light scattering (DLS), and the morphology of the polyplexes was obtained using atomic force microscopy (AFM). All the PAAs were able to condense pDNA into nanoparticles with diameters between 50 and 200 nm with a positive surface charge when the weight ratio of polymer/DNA was higher than 20. Glutathione (GSH)-induced DNA release from polyplexes and the buffering capability of PAAs were investigated as well. Cytotoxicity of PAAs and in vitro gene transfection of polyplexes were evaluated in HEK293, COS-7, MCF-7 and Hep G2 cell lines, respectively. The results reflect that PAAs show remarkably low or even no cytotoxicity, and that PAA with amino terminal groups mediates the most efficient gene transfection with the transfection efficiency comparable to that of 25 kDa polyethylenimine. Further the effects of the presence of buthionine sulfoximine (BSO) on the transfection efficiency and cytotoxicity of BAA polyplexes were investigated.