Oxygen-Bridged Indium-Nickel Atomic Pair as Dual-Metal Active Sites Enabling Synergistic Electrocatalytic CO2 Reduction.

Single-atom catalysts offer a promising pathway for electrochemical CO2 conversion. However, it is still a challenge to optimize the electrochemical performance of dual-atom catalysts. Here, an atomic indium-nickel dual-sites catalyst bridged by an axial oxygen atom (O-In-N6 -Ni moiety) was anchored on nitrogenated carbon (InNi DS/NC). InNi DS/NC exhibits superior CO selectivity with Faradaic efficiency higher than 90 % over a wide potential range from -0.5 to -0.8 V versus reversible hydrogen electrode (vs. RHE). Moreover, an industrial CO partial current density up to 317.2 mA cm-2 is achieved at -1.0 V vs. RHE in a flow cell. In situ ATR-SEIRAS combined with theory calculations reveal that the synergistic effect of In-Ni dual-sites and O atom bridge not only reduces the reaction barrier for the formation of *COOH, but also retards the undesired hydrogen evolution reaction. This work provides a feasible strategy to construct dual-site catalysts towards energy conversion.

Engineering Single-Atomic Ni-N4-O Sites on Semiconductor Photoanodes for High-Performance Photoelectrochemical Water Splitting.

Direct photoelectrochemical (PEC) water splitting is a promising solution for solar energy conversion; however, there is a pressing bottleneck to address the intrinsic charge transport for the enhancement of PEC performance. Herein, a versatile coupling strategy was developed to engineer atomically dispersed Ni-N4 sites coordinated with an axial direction oxygen atom (Ni-N4-O) incorporated between oxygen evolution cocatalyst (OEC) and semiconductor photoanode, boosting the photogenerated electron-hole separation and thus improving PEC activity. This state-of-the-art OEC/Ni-N4-O/BiVO4 photoanode exhibits a record high photocurrent density of 6.0 mA cm-2 at 1.23 V versus reversible hydrogen electrode (vs RHE), over approximately 3.97 times larger than that of BiVO4, achieving outstanding long-term photostability. From X-ray absorption fine structure analysis and density functional theory calculations, the enhanced PEC performance is attributed to the construction of single-atomic Ni-N4-O moiety in OEC/BiVO4, facilitating the holes transfer, decreasing the free energy barriers, and accelerating the reaction kinetics. This work enables us to develop an effective pathway to design and fabricate efficient and stable photoanodes for feasible PEC water splitting application.

Engineering Lattice Oxygen Activation of Iridium Clusters Stabilized on Amorphous Bimetal Borides Array for Oxygen Evolution Reaction.

Developing robust oxygen evolution reaction (OER) catalysts requires significant advances in material design and in-depth understanding for water electrolysis. Herein, we report iridium clusters stabilized surface reconstructed oxyhydroxides on amorphous metal borides array, achieving an ultralow overpotential of 178 mV at 10 mA cm-2 for OER in alkaline medium. The coupling of iridium clusters induced the formation of high valence cobalt species and Ir-O-Co bridge between iridium and oxyhydroxides at the atomic scale, engineering lattice oxygen activation and non-concerted proton-electron transfer to trigger multiple active sites for intrinsic pH-dependent OER activity. The lattice oxygen oxidation mechanism (LOM) was confirmed by in situ 18 O isotope labeling mass spectrometry and chemical recognition of negative peroxo-like species. Theoretical simulations reveal that the OER performance on this catalyst is intrinsically dominated by LOM pathway, facilitating the reaction kinetics. This work not only paves an avenue for the rational design of electrocatalysts, but also serves the fundamental insights into the lattice oxygen participation for promising OER application.

Two-Dimensional Defective Boron-Doped Niobic Acid Nanosheets for Robust Nitrogen Photofixation.

Direct nitrogen photofixation is a feasible solution toward sustainable production of ammonia under mild conditions. However, the generation of active sites for solar-dirven nitrogen fixation not only limits the fundamental understanding of the relationship among light absorption, charge transfer, and catalytic efficiency but also influences the photocatalytic activity. Herein, we report two-dimensional boron-doped niobic acid nanosheets with oxygen vacancies (B-Vo-HNbO3 NSs) for efficient N2 photofixation in the absence of any scavengers and cocatalysts. Impressively, B-Vo-HNbO3 NS as a model catalyst achieves the enhanced ammonia evolution rate of 170 µmol gcat-1 h-1 in pure water under visible-light irradiation. The doublet coupling representing 15NH4+ in an isotopic labeling experiment and in situ infrared spectra confirm the reliable ammonia generation. The experimental analysis and density functional theory (DFT) calculations indicate that the strong synergy of boron dopant and oxygen vacancy regulates band structure of niobic acid, facilitates photogenerated charge transfer, reduces free energy barriers, accelerates reaction kinetics, and promotes the high rates of ammonia evolution. This work provides a general strategy to design active photocatalysts toward solar N2 conversion.

Engineering single-atomic ruthenium catalytic sites on defective nickel-iron layered double hydroxide for overall water splitting.

Rational design of single atom catalyst is critical for efficient sustainable energy conversion. However, the atomic-level control of active sites is essential for electrocatalytic materials in alkaline electrolyte. Moreover, well-defined surface structures lead to in-depth understanding of catalytic mechanisms. Herein, we report a single-atomic-site ruthenium stabilized on defective nickel-iron layered double hydroxide nanosheets (Ru1/D-NiFe LDH). Under precise regulation of local coordination environments of catalytically active sites and the existence of the defects, Ru1/D-NiFe LDH delivers an ultralow overpotential of 18 mV at 10 mA cm-2 for hydrogen evolution reaction, surpassing the commercial Pt/C catalyst. Density functional theory calculations reveal that Ru1/D-NiFe LDH optimizes the adsorption energies of intermediates for hydrogen evolution reaction and promotes the O-O coupling at a Ru-O active site for oxygen evolution reaction. The Ru1/D-NiFe LDH as an ideal model reveals superior water splitting performance with potential for the development of promising water-alkali electrocatalysts.

Numerical calculation of a converging vector electromagnetic wave diffracted by an aperture using Borgnis potentials. II. Application to the study of focal shift.

Focal shift of the converging spherical wavefront light diffracted by a circular aperture is numerically studied with the method of calculating the vector diffractive field by using Borgnis potentials given in Part I [J. Opt. Soc. Am. A23, 872 (2006)]. The quantitative dependence of the focal shift on the geometric parameters is discussed. The focal shift is mainly determined by the Fresnel number (N(f)) on the geometric focusing plane of the converging light, and an empirical formula between the fractional focal shift and the Fresnel number is deduced for N(f)<2. The focal shift of the same geometry is also studied on the basis of the scalar Rayleigh theory of diffraction, and its comparison with and difference from the result of our method are presented.

Numerical calculation of a converging vector electromagnetic wave diffracted by an aperture by using Borgnis potentials. I. General theory.

A method is proposed, on the basis of the vector electromagnetic theory, for the numerical calculation of the diffraction of a converging electromagnetic wave by a circular aperture by using Borgnis potentials as auxiliary functions. The diffraction problem of vector electromagnetic fields is simplified greatly by solving the scalar Borgnis potentials. The diffractive field is calculated on the basis of the boundary integral equation, taking into consideration the contribution of the field variables on the diffraction screen surface, which is ignored in the Kirchhoff assumption. An example is given to show the effectiveness and suitability of this method and the distinctiveness of the diffractive fields caused by the vector characteristics of the electromagnetic fields.

Vector near-field calculation of scanning near-field optical microscopy probes using Borgnis potentials as auxiliary functions.

A new boundary integral equation method for solving the near field in three-dimensional vector form in scanning near-field optical microscopy (SNOM) using Borgnis potentials as auxiliary functions is presented. A boundary integral equation of the electromagnetic fields, expressed by Borgnis potentials, is derived based on Green's theorem. The harmonic expansion in rotationally symmetric SNOM probe--sample systems is studied, and the three-dimensional electromagnetic problem is partly simplified into a two-dimensional one. The boundary conditions of Borgnis potentials both on dielectric boundaries and on perfectly conducting boundaries are derived. Relevant algorithms were studied, and a computer program was written. As an example, a SNOM probe-sample system composed of a round metal-covered probe and a sample with a flat surface has been numerically studied, and the computational results are given. This new method can be used efficiently for other electromagnetic field problems with round subwavelength structures.

Simulation of topographic images and artifacts in illumination-mode scanning-near-field optical microscopy.

Scanning images in illumination-mode, scanning-near-field optical microscopy (SNOM) are numerically studied by the boundary element method based on rigorous vector electromagnetic theory. Computation results of constant-height and constant-distance images for samples with different topographic features are presented. Effects of the polarization of the input light and the optical parameters of samples on the resolution of SNOM are discussed. The artifacts in constant-distance images are also investigated. Numerical results indicate that the constant-height images for TM input light and constant-distance images for both TE and TM input light give only the local changes of the sample topography because of the loss of the low-frequency component of the topography.