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.

Engineering FeCo Dual Sites on Tube-on-Plate Hollow Structure for Efficient Oxygen Electroreduction.

Atomically dispersed single-atom catalysts are intriguing catalysts in the field of electrocatalysis for nearly 100% exploitation of metal atoms. However, they are still far from practical usage due to the scaling relationship limit and metal loading limit. Generation of a diatomic complex would offer superior catalytic performance through the cooperation of two neighboring atoms as active sites. Herein, Fe/Co dual atomic sites embedded in a tube-on-plate hollow structure are designed and fabricated for an efficient electrochemical oxygen reduction reaction (ORR). The unique structure composed of ultrathin nanotube building blocks dramatically maximizes the surface area for copious active site exposure. Thanks to the synergetic interaction between Fe/Co pairs, the obtained FeCo/NC exhibits outstanding ORR activity and stability in alkaline media. Furthermore, density functional theory calculations have revealed that the remarkable activity is attributed to the electron-deficient Fe sites in FeCoN6. This work may pave the way for the innovative design of highly dispersed dual-site catalysts for broader applications in the realm of electrochemical catalysis.

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.

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.

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.

Atomic-Level Interface Engineering for Boosting Oxygen Electrocatalysis Performance of Single-Atom Catalysts: From Metal Active Center to the First Coordination Sphere.

Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are the core reactions of a series of advanced modern energy and conversion technologies, such as fuel cells and metal-air cells. Among all kinds of oxygen electrocatalysts that have been reported, single-atom catalysts (SACs) offer great development potential because of their nearly 100% atomic utilization, unsaturated coordination environment, and tunable electronic structure. In recent years, numerous SACs with enriched active centers and asymmetric coordination have been successfully constructed by regulating their coordination environment and electronic structure, which has brought the development of atomic catalysts to a new level. This paper reviews the improvement of SACs brought by atom-level interface engineering. It starts with the introduction of advanced techniques for the characterizations of SACs. Subsequently, different design strategies that are applied to adjust the metal active center and first coordination sphere of SACs and then enhance their oxygen electrocatalysis performance are systematically illustrated. Finally, the future development of SACs toward ORR and OER is discussed and prospected.

Regulating the scaling relationship for high catalytic kinetics and selectivity of the oxygen reduction reaction.

The electrochemical oxygen reduction reaction (ORR) is at the heart of modern sustainable energy technologies. However, the linear scaling relationship of this multistep reaction now becomes the bottleneck for accelerating kinetics. Herein, we propose a strategy of using intermetallic-distance-regulated atomic-scale bimetal assembly (ABA) that can catalyse direct O‒O radical breakage without the formation of redundant *OOH intermediates, which could regulate the inherent linear scaling relationship and cause the ORR on ABA to follow a fast-kinetic dual-sites mechanism. Using in situ synchrotron spectroscopy, we directly observe that a self-adjustable N-bridged Pt = N2 = Fe assembly promotes the generation of a key intermediate state (Pt‒O‒O‒Fe) during the ORR process, resulting in high reaction kinetics and selectivity. The well-designed Pt = N2 = Fe ABA catalyst achieves a nearly two orders of magnitude enhanced kinetic current density at the half-wave potential of 0.95 V relative to commercial Pt/C and an almost 99% efficiency of 4-electron pathway selectivity, making it one of the potential ORR catalysts for application to the energy device of zinc‒air cells. This study provides a helpful design principle for developing and optimizing other efficient ORR electrocatalysts.

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.

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.

Recent Advances in Dual-Atom Site Catalysts for Efficient Oxygen and Carbon Dioxide Electrocatalysis.

Atomically dispersed metal catalysts have been widely used in electrocatalysis because of their outstanding catalytic activity and high atomic utilization efficiency. As an extension of single-atom catalysts (SACs), dual-atom catalysts (DACs) provide new insights for the development of atomic-scale catalysts. Higher metal loading and more flexible active sites endow DACs with improved catalytic performance as well as optimized reaction mechanism model. In this review, DACs are firstly classified according to their configurations and metal sites. Subsequently, the synthetic strategies and characterization techniques of DACs are introduced. Furthermore, the applications of DACs are exemplified in various electrocatalytic reactions, including oxygen reduction reaction, oxygen evolution reaction and carbon dioxide reduction reaction. Finally, the prospects to be expected and challenges to be faced with are discussed.

Loading Single-Ni Atoms on Assembled Hollow N-Rich Carbon Plates for Efficient CO2 Electroreduction.

The rational design of catalysts' spatial structure is vitally important to boost catalytic performance through exposing the active sites, enhancing the mass transfer, and confining the reactants. Herein, a dual-linker zeolitic tetrazolate framework-engaged strategy is developed to construct assembled hollow plates (AHP) of N-rich carbon (NC), which is loaded with single-Ni atoms to form a highly efficient electrocatalyst (designated as Ni-NC(AHP)). In the carbonization process, the thermally unstable linker (5-aminotetrazole) serves as the self-sacrificial template and the other linker (2-methylimidazole) mainly serves as the carbon and nitrogen source to form hollow NC matrix. The formed Ni-NC(AHP) catalyst possesses enhanced mesoporosity and more available surface area, thus promoting mass transport and affording abundant accessible single-Ni sites. These features contribute to remarkable performance for electrochemical CO2 reduction with exceptionally high selectivity of nearly 100% towards CO in a wide potential range and dramatically enhanced CO partial current density.

In Situ Construction of Flexible VNi Redox Centers over Ni-Based MOF Nanosheet Arrays for Electrochemical Water Oxidation.

Atomic-level design and construction of synergistic active centers are central to develop advanced oxygen electrocatalysts toward efficient energy conversion. Herein, an in situ construction strategy to introduce flexible redox sites of VNi centers onto Ni-based metal-organic framework (MOF) nanosheet arrays (NiV-MOF NAs) as a promising oxygen electrocatalyst is developed. The abundant redox VNi centers with flexible metal valence states of V+3/+4/+5 and Ni+3/+2 enable NiV-MOF NAs excellent oxygen evolution reaction (OER) activity and a long-term stability under high current densities, achieving current densities of 10 and 100 mA cm-2 at recorded overpotentials of 189 and 290 mV, respectively, and showing ignorable decay of initial activity at 100 mA cm-2 after 100 h OER operation. Operando synchrotron radiation Fourier transform infrared combined with quasi in situ X-ray absorption fine structure spectroscopies reveal at atomic level that the flexible V sites can continuously accept electrons from adjacent active Ni sites to accelerate OER kinetics for NiV-MOF NAs during the reaction process, accompanied by a self-optimized structural distortion of VO6 octahedron for promoting the electrochemical stability.

In situ activation of Br-confined Ni-based metal-organic framework hollow prisms toward efficient electrochemical oxygen evolution.

Fundamental insights into the structural evolution of oxygen electrocatalysts under operating conditions are of substantial importance for designing efficient catalysts. Here, on the basis of operando x-ray absorption fine structure spectroscopy, we probe the in situ activation of Br-confined conductive Ni-based metal-organic framework (Br-Ni-MOF) hollow prisms toward an active oxygen electrocatalyst during the oxygen evolution reaction (OER) process. The successive structural transformations from pristine Br-Ni-MOF to a ß-Ni(OH)2 analog then subsequently to a γ-NiOOH phase during OER are observed. This post-formed γ-NiOOH analog manifests high OER performance with a superior overpotential of 306 mV at 10 mA cm−2 and a high turnover frequency value of 0.051 s−1 at an overpotential of 300 mV, making Br-Ni-MOF one of the most active oxygen electrocatalysts reported. Density functional theory calculations reveal that the strong electronic coupling between Br and Ni atoms accelerates the generation of the key *O intermediate toward fast OER kinetics.

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.

Self-Nanocavity-Confined Halogen Anions Boosting the High Selectivity of the Two-Electron Oxygen Reduction Pathway over Ni-Based MOFs.

We present a strategy of self-nanocavity confinement for substantially boosting the superior electrochemical hydrogen peroxide (H2O2) selectivity for conductive metal-organic framework (MOF) materials. By using operando synchrotron radiation X-ray adsorption fine structure and Fourier transform infrared spectroscopy analyses, the dissociation of key *OOH intermediates during the oxygen reduction reaction (ORR) is effectively suppressed over the self-nanocavity-confined X-Ni MOF (X = F, Cl, Br, or I) catalysts, contributing to a favorable two-electron ORR pathway for highly efficient H2O2 production. As a result, the as-prepared Br-confined Ni MOF catalyst significantly promotes H2O2 selectivity up to 90% in an alkaline solution, evidently outperforming the pristine Ni MOF catalyst (40%). Moreover, a maximal faradic efficiency of 86% with a high cumulative H2O2 yield rate of 596 mmol gcatalyst-1 h-1 for electrochemical H2O2 generation is achieved by the Br-confined Ni MOF catalyst.

Exposing unsaturated Cu1-O2 sites in nanoscale Cu-MOF for efficient electrocatalytic hydrogen evolution.

Conductive metal-organic framework (MOF) materials have been recently considered as effective electrocatalysts. However, they usually suffer from two major drawbacks, poor electrochemical stability and low electrocatalytic activity in bulk form. Here, we have developed a rational strategy to fabricate a promising electrocatalyst composed of a nanoscale conductive copper-based MOF (Cu-MOF) layer fully supported over synergetic iron hydr(oxy)oxide [Fe(OH) x ] nanoboxes. Owing to the highly exposed active centers, enhanced charge transfer, and robust hollow nanostructure, the obtained Fe(OH) x @Cu-MOF nanoboxes exhibit superior activity and stability for the electrocatalytic hydrogen evolution reaction (HER). Specifically, it needs an overpotential of 112 mV to reach a current density of 10 mA cm-2 with a small Tafel slope of 76 mV dec-1 X-ray absorption fine structure spectroscopy combined with density functional theory calculations unravels that the highly exposed coordinatively unsaturated Cu1-O2 centers could effectively accelerate the formation of key *H intermediates toward fast HER 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.

Face Masks in the New COVID-19 Normal: Materials, Testing, and Perspectives.

The increasing prevalence of infectious diseases in recent decades has posed a serious threat to public health. Routes of transmission differ, but the respiratory droplet or airborne route has the greatest potential to disrupt social intercourse, while being amenable to prevention by the humble face mask. Different types of masks give different levels of protection to the user. The ongoing COVID-19 pandemic has even resulted in a global shortage of face masks and the raw materials that go into them, driving individuals to self-produce masks from household items. At the same time, research has been accelerated towards improving the quality and performance of face masks, e.g., by introducing properties such as antimicrobial activity and superhydrophobicity. This review will cover mask-wearing from the public health perspective, the technical details of commercial and home-made masks, and recent advances in mask engineering, disinfection, and materials and discuss the sustainability of mask-wearing and mask production into the future.

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.

Coupling N2 and CO2 in H2O to synthesize urea under ambient conditions.

The use of nitrogen fertilizers has been estimated to have supported 27% of the world's population over the past century. Urea (CO(NH2)2) is conventionally synthesized through two consecutive industrial processes, N2 + H2 → NH3 followed by NH3 + CO2 → urea. Both reactions operate under harsh conditions and consume more than 2% of the world's energy. Urea synthesis consumes approximately 80% of the NH3 produced globally. Here we directly coupled N2 and CO2 in H2O to produce urea under ambient conditions. The process was carried out using an electrocatalyst consisting of PdCu alloy nanoparticles on TiO2 nanosheets. This coupling reaction occurs through the formation of C-N bonds via the thermodynamically spontaneous reaction between *N=N* and CO. Products were identified and quantified using isotope labelling and the mechanism investigated using isotope-labelled operando synchrotron-radiation Fourier transform infrared spectroscopy. A high rate of urea formation of 3.36 mmol g-1 h-1 and corresponding Faradic efficiency of 8.92% were measured at -0.4 V versus reversible hydrogen electrode.