Self-adaptive integration of photothermal and radiative cooling for continuous energy harvesting from the sun and outer space.

The sun (∼6,000 K) and outer space (∼3 K) are two significant renewable thermodynamic resources for human beings on Earth. The solar thermal conversion by photothermal (PT) and harvesting the coldness of outer space by radiative cooling (RC) have already attracted tremendous interest. However, most of the PT and RC approaches are static and monofunctional, which can only provide heating or cooling respectively under sunlight or darkness. Herein, a spectrally self-adaptive absorber/emitter (SSA/E) with strong solar absorption and switchable emissivity within the atmospheric window (i.e., 8 to 13 µm) was developed for the dynamic combination of PT and RC, corresponding to continuously efficient energy harvesting from the sun and rejecting energy to the universe. The as-fabricated SSA/E not only can be heated to ∼170 °C above ambient temperature under sunshine but also be cooled to 20 °C below ambient temperature, and thermal modeling captures the high energy harvesting efficiency of the SSA/E, enabling new technological capabilities.

Constructing Asymmetric Charge Polarized NiCo Prussian Blue Analogue for Promoted Electrocatalytic Methanol to Formate Conversion.

The highly selective electrochemical conversion of methanol to formate is of great significance for various clean energy devices, but understanding the structure-to-property relationship remains unclear. Here, the asymmetric charge polarized NiCo prussian blue analogue (NiCo PBA-100) is reported to exhibit remarkable catalytic performance with high current density (210 mA cm-2 @1.65 V vs RHE) and Faraday efficiency (over 90%). Meanwhile, the hybrid water splitting and Zinc-methanol-battery assembled by NiCo PBA-100 display the promoted performance with decent stability. X-ray absorption spectroscopy (XAS) and operando Raman spectroscopy indicate that the asymmetric charge polarization in NiCo PBA leads to more unoccupied states of Ni and occupied states of Co, thereby facilitating the rapid transformation of the high-active catalytic centers. Density functional theory calculations combining operando Fourier transform infrared spectroscopy demonstrate that the final reconstructed catalyst derived by NiCo PBA-100 exhibits rearranged d band properties along with a lowered energy barrier of the rate-determining step and favors the desired formate production.

Operando Direct Observation of Stable Water-Oxidation Intermediates on Ca2-xIrO4 Nanocrystals for Efficient Acidic Oxygen Evolution.

We report Ca2-xIrO4 nanocrystals exhibit record stability of 300 h continuous operation and high iridium mass activity (248 A gIr-1 at 1.5 VRHE) that is about 62 times that of benchmark IrO2. Lattice-resolution images and surface-sensitive spectroscopies demonstrate the Ir-rich surface layer (evolved from one-dimensional connected edge-sharing [IrO6] octahedrons) with high relative content of Ir5+ sites, which is responsible for the high activity and long-term stability. Combining operando infrared spectroscopy with X-ray absorption spectroscopy, we report the first direct observation of key intermediates absorbing at 946 cm-1 (Ir6+═O site) and absorbing at 870 cm-1 (Ir6+OO- site) on iridium-based oxides electrocatalysts, and further discover the Ir6+═O and Ir6+OO- intermediates are stable even just from 1.3 VRHE. Density functional theory calculations indicate the catalytic activity of Ca2IrO4 is enhanced remarkably after surface Ca leaching, and suggest IrOO- and Ir═O intermediates can be stabilized on positive charged active sites of Ir-rich surface layer.

Pd-Modified ZnO-Au Enabling Alkoxy Intermediates Formation and Dehydrogenation for Photocatalytic Conversion of Methane to Ethylene.

Photocatalysis provides an intriguing approach for the conversion of methane to multicarbon (C2+) compounds under mild conditions; however, with methyl radicals as the sole reaction intermediate, the current C2+ products are dominated by ethane, with a negligible selectivity toward ethylene, which, as a key chemical feedstock, possesses higher added value than ethane. Herein, we report a direct photocatalytic methane-to-ethylene conversion pathway involving the formation and dehydrogenation of alkoxy (i.e., methoxy and ethoxy) intermediates over a Pd-modified ZnO-Au hybrid catalyst. On the basis of various in situ characterizations, it is revealed that the Pd-induced dehydrogenation capability of the catalyst holds the key to turning on the pathway. During the reaction, methane molecules are first dissociated into methoxy on the surface of ZnO under the assistance of Pd. Then these methoxy intermediates are further dehydrogenated and coupled with methyl radical into ethoxy, which can be subsequently converted into ethylene through dehydrogenation. As a result, the optimized ZnO-AuPd hybrid with atomically dispersed Pd sites in the Au lattice achieves a methane conversion of 536.0 µmol g-1 with a C2+ compound selectivity of 96.0% (39.7% C2H4 and 54.9% C2H6 in total produced C2+ compounds) after 8 h of light irradiation. This work provides fresh insight into the methane conversion pathway under mild conditions and highlights the significance of dehydrogenation for enhanced photocatalytic activity and unsaturated hydrocarbon product selectivity.

Efficient Photoelectrochemical Conversion of Methane into Ethylene Glycol by WO3 Nanobar Arrays.

Photoelectrochemical (PEC) conversion of methane (CH4 ) has been extensively explored for the production of value-added chemicals, yet remains a great challenge in high selectivity toward C2+ products. Herein, we report the optimization of the reactivity of hydroxyl radicals (. OH) on WO3 via facet tuning to achieve efficient ethylene glycol production from PEC CH4 conversion. A combination of materials simulation and radicals trapping test provides insight into the reactivity of . OH on different facets of WO3 , showing the highest reactivity of surface-bound . OH on {010} facets. As such, the WO3 with the highest {010} facet ratio exhibits a superior PEC CH4 conversion efficiency, reaching an ethylene glycol production rate of 0.47 µmol cm-2 h-1 . Based on in situ characterization, the methanol, which could be attacked by reactive . OH to form hydroxymethyl radicals, is confirmed to be the main intermediate for the production of ethylene glycol. Our finding is expected to provide new insight for the design of active and selective catalysts toward PEC CH4 conversion.

Single-Atom-Layer Catalysis in a MoS2 Monolayer Activated by Long-Range Ferromagnetism for the Hydrogen Evolution Reaction: Beyond Single-Atom Catalysis.

Single-atom-layer catalysts with fully activated basal-atoms will provide a solution to the low loading-density bottleneck of single-atom catalysts. Herein, we activate the majority of the basal sites of monolayer MoS2 , by doping Co ions to induce long-range ferromagnetic order. This strategy, as revealed by in situ synchrotron radiation microscopic infrared spectroscopy and electrochemical measurements, could activate more than 50 % of the originally inert basal-plane S atoms in the ferromagnetic monolayer for the hydrogen evolution reaction (HER). Consequently, on a single monolayer of ferromagnetic MoS2 measured by on-chip micro-cell, a current density of 10 mA cm-2 could be achieved at the overpotential of 137 mV, corresponding to a mass activity of 28, 571 Ag-1 , which is two orders of magnitude higher than the multilayer counterpart. Its exchange current density of 75 µA cm-2 also surpasses most other MoS2 -based catalysts. Experimental results and theoretical calculations show the activation of basal plane S atoms arises from an increase of electronic density around the Fermi level, promoting the H adsorption ability of basal-plane S atoms.

Anchoring Positively Charged Pd Single Atoms in Ordered Porous Ceria to Boost Catalytic Activity and Stability in Suzuki Coupling Reactions.

Single-atom (SA) catalysis bridging homogeneous and heterogeneous catalysis offers new opportunities for organic synthesis, but developing SA catalysts with high activity and stability is still a great challenge. Herein, a heterogeneous catalyst of Pd SAs anchored in 3D ordered macroporous ceria (Pd-SAs/3DOM-CeO2 ) is developed through a facile template-assisted pyrolysis method. The high specific surface area of 3DOM CeO2 facilitates the heavily anchoring of Pd SAs, while the introduction of Pd atoms induces the generation of surface oxygen vacancies and prevents the grain growth of CeO2 support. The Pd-SAs/3DOM-CeO2 catalyst exhibits excellent activity toward Suzuki coupling reactions for a broad scope of substrates under ambient conditions, and the Pd SAs can be stabilized in CeO2 in long-term catalytic cycles without leaching or aggregating. Theoretical calculations indicate that the CeO2 supported Pd SAs can remarkably reduce the energy barriers of both transmetalation and reductive elimination steps for Suzuki coupling reactions. The strong metal-support interaction contributes to modulating the electronic state and maintaining the stability of Pd SA sites. This work demonstrates an effective strategy to design and synthesize stable single-atom catalysts as well as sheds new light on the origin for enhanced catalysis based on the strong metal-support interactions.

Site Occupancies, VUV-UV-vis Photoluminescence, and X-ray Radioluminescence of Eu2+-Doped RbBaPO4.

RbBaPO4:Eu2+ phosphors have been prepared by a high-temperature solid-state reaction method, and the structure was determined by Rietveld refinement based on powder X-ray diffraction (P-XRD) data. Their VUV-UV-vis photoluminescence properties are systematically investigated with three objectives: (1) based on low-temperature spectra, we clarify the site occupancies of Eu2+, and demonstrate that the doublet emission bands at ∼406 and ∼431 nm originate from Eu2+ in Ba2+ [Eu2+(I)] and Rb+ [Eu2+(II)] sites, respectively; (2) an electron-vibrational interaction (EVI) analysis is conducted to estimate the Huang-Rhys factors, the zero-phonon lines (ZPLs) and the Stokes shifts of Eu2+ in Rb+ and Ba2+ sites; (3) the studies on luminescence decay of Eu2+(I) reveal that dipole-dipole interaction is mainly responsible for the energy transfer from Eu2+(I) to Eu2+(II), and the energy migration between Eu2+(I) is weak. Finally, the X-ray excited luminescence (XEL) spectrum indicates that the light yield of the sample RbBa0.995Eu0.005PO4 is ∼17 700 ph/MeV, showing its potential application in X-ray detecting.

Surface Plasmon Enabling Nitrogen Fixation in Pure Water through a Dissociative Mechanism under Mild Conditions.

Nitrogen fixation in a simulated natural environment (i.e., near ambient pressure, room temperature, pure water, and incident light) would provide a desirable approach to future nitrogen conversion. As the N≡N triple bond has a thermodynamically high cleavage energy, nitrogen reduction under such mild conditions typically undergoes associative alternating or distal pathways rather than following a dissociative mechanism. Here, we report that surface plasmon can supply sufficient energy to activate N2 through a dissociative mechanism in the presence of water and incident light, as evidenced by in situ synchrotron radiation-based infrared spectroscopy and near ambient pressure X-ray photoelectron spectroscopy. Theoretical simulation indicates that the electric field enhanced by surface plasmon, together with plasmonic hot electrons and interfacial hybridization, may play a critical role in N≡N dissociation. Specifically, AuRu core-antenna nanostructures with broadened light adsorption cross section and active sites achieve an ammonia production rate of 101.4 µmol g-1 h-1 without any sacrificial agent at room temperature and 2 atm pressure. This work highlights the significance of surface plasmon to activation of inert molecules, serving as a promising platform for developing novel catalytic systems.

Quantum Control of Graphene Plasmon Excitation and Propagation at Heaviside Potential Steps.

Quantum mechanical effects of single particles can affect the collective plasmon behaviors substantially. In this work, the quantum control of plasmon excitation and propagation in graphene is demonstrated by adopting the variable quantum transmission of carriers at Heaviside potential steps as a tuning knob. First, the plasmon reflection is revealed to be tunable within a broad range by varying the ratio γ between the carrier energy and potential height, which originates from the quantum mechanical effect of carrier propagation at potential steps. Moreover, the plasmon excitation by free-space photos can be regulated from fully suppressed to fully launched in graphene potential wells also through adjusting γ, which defines the degrees of the carrier confinement in the potential wells. These discovered quantum plasmon effects offer a unified quantum-mechanical solution toward ultimate control of both plasmon launching and propagating, which are indispensable processes in building plasmon circuitry.

Refining Defect States in W18O49 by Mo Doping: A Strategy for Tuning N2 Activation towards Solar-Driven Nitrogen Fixation.

Photocatalysis may provide an intriguing approach to nitrogen fixation, which relies on the transfer of photoexcited electrons to the ultrastable N≡N bond. Upon N2 chemisorption at active sites (e.g., surface defects), the N2 molecules have yet to receive energetic electrons toward efficient activation and dissociation, often forming a bottleneck. Herein, we report that the bottleneck can be well tackled by refining the defect states in photocatalysts via doping. As a proof of concept, W18O49 ultrathin nanowires are employed as a model material for subtle Mo doping, in which the coordinatively unsaturated (CUS) metal atoms with oxygen defects serve as the sites for N2 chemisorption and electron transfer. The doped low-valence Mo species play multiple roles in facilitating N2 activation and dissociation by refining the defect states of W18O49: (1) polarizing the chemisorbed N2 molecules and facilitating the electron transfer from CUS sites to N2 adsorbates, which enables the N≡N bond to be more feasible for dissociation through proton coupling; (2) elevating defect-band center toward the Fermi level, which preserves the energy of photoexcited electrons for N2 reduction. As a result, the 1 mol % Mo-doped W18O49 sample achieves an ammonia production rate of 195.5 µmol gcat-1 h-1, 7-fold higher than that of pristine W18O49. In pure water, the catalyst demonstrates an apparent quantum efficiency of 0.33% at 400 nm and a solar-to-ammonia efficiency of 0.028% under simulated AM 1.5 G light irradiation. This work provides fresh insights into the design of photocatalyst lattice for N2 fixation and reaffirms the versatility of subtle electronic structure modulation in tuning catalytic activity.

Unambiguous Identification of Carbon Location on the N Site in Semi-insulating GaN.

Carbon (C) doping is essential for producing semi-insulating GaN for power electronics. However, to date the nature of C doped GaN, especially the lattice site occupation, is not yet well understood. In this work, we clarify the lattice site of C in GaN using polarized Fourier-transform infrared and Raman spectroscopies, in combination with first-principles calculations. Two local vibrational modes (LVMs) at 766 and 774 cm^{-1} in C doped GaN are observed. The 766 cm^{-1} mode is assigned to the nondegenerate A_{1} mode vibrating along the c axis, whereas the 774 cm^{-1} mode is ascribed to the doubly degenerate E mode confined in the plane perpendicular to the c axis. The two LVMs are identified to originate from isolated C_{N}^{-} with local C_{3v} symmetry. Experimental data and calculations are in outstanding agreement both for the positions and the intensity ratios of the LVMs. We thus provide unambiguous evidence of the substitutional C atoms occupying the N site with a -1 charge state in GaN and therefore bring essential information to a long-standing controversy.

Surface Modification on Pd-TiO2 Hybrid Nanostructures towards Highly Efficient H2 Production from Catalytic Formic Acid Decomposition.

Metal-containing nanocrystals with well-designed surface structures represent a class of model systems for revealing the fundamental physical and chemical processes involved in heterogeneous catalysis. Herein it is shown how surface modification can be utilized as an efficient strategy for controlling the surface electronic state of catalysts and, thus, for tuning their catalytic activity. As model catalysts, the Pd-tetrahedron-TiO2 nanostructures, modified on the surface with different foreign atoms, showed a varied activity in the catalytic decomposition of formic acid towards H2 production. The catalytic activity increases with a reduction in the work function of modified atoms; this reduction can be well explained by a surface polarization mechanism. In this hybrid system, the difference in the work functions of Pd and modified atoms results in surface polarization on the Pd surface and, thus, in the tuning of its charge state. Together with the Schottky junction between TiO2 and metals, the tuned charge state enables the promotion of catalytic efficiency in the catalytic decomposition of formic acid to H2 and CO2 .

Stretch-induced complexation reaction between poly(vinyl alcohol) and iodine: an in situ synchrotron radiation small- and wide-angle X-ray scattering study.

Fibrillation and the complexation reaction between poly(vinyl alcohol) (PVA)-iodine (i) complexes have been studied with in situ synchrotron radiation small- and wide-angle X-ray scattering (SAXS and WAXS) during the uniaxial stretching of PVA films in KI/I2 aqueous solution. SAXS results show that stretching induces the formation of nanofibrils, which pack periodically in the later stage of stretching with an average inter-fibrillar distance of around 10 nm. The onset strains for fibrillation and the appearance of periodicity of nanofibrils are located at the beginning and the end of the stress plateau, and decrease with increasing iodine concentration. In the stretching process as a whole, the presence of iodine ions reduces the crystallinity of the PVA crystal but favors the formation of a PVA-I complex. The complexation reaction is promoted by the synergistic effect of stretch and iodine ions, during which stretching drives the formation of polyiodine via the effect of entropic reduction while iodine concentration dictates crystallization of PVA-I3- co-crystals through the role of chemical potential. A morphological and structural phase diagram is constructed in the strain-iodine concentration space, which defines the regions for fibrillation and complexation reactions and may serve as a roadmap for the industrial processing of PVA polarizer.

Internal Relations between Crystal Structures and Intrinsic Properties of Nonstoichiometric Ba1+ xMoO4 Ceramics.

Ba1+ xMoO4 (-0.03 ≤ x ≤ 0.03) ceramics were fabricated by a conventional two-step sintering technique. X-ray diffraction patterns show that there appeared new diffraction peaks when x > 0, which were identified as Ba2MoO5. The Rietveld refinement results indicate that the unit cell volume is the largest at x = -0.02, because it has the lowest packing fraction and covalency. The far-infrared reflectivity (IR) spectra were fitted and analyzed for calculating the intrinsic properties, which comply well with the data obtained from microscopic polarizabilities and damping coefficient angle. The proportion of each mode in the dielectric response demonstrates that the Ba-O8 polyhedra have a decisive role on the dielectric properties. And based on the Raman modes, the internal relations of the structural-properties were revealed with the changes of Ba2+ content.

Application of far-infrared spectroscopy to the structural identification of protein materials.

Although far-infrared (IR) spectroscopy has been shown to be a powerful tool to determine peptide structure and to detect structural transitions in peptides, it has been overlooked in the characterization of proteins. Herein, we used far-IR spectroscopy to monitor the structure of four abundant non-bioactive proteins, namely, soybean protein isolate (SPI), pea protein isolate (PPI) and two types of silk fibroins (SFs), domestic Bombyx mori and wild Antheraea pernyi. The two globular proteins SPI and PPI result in broad and weak far-IR bands (between 50 and 700 cm-1), in agreement with those of some other bioactive globular proteins previously studied (lysozyme, myoglobin, hemoglobin, etc.) that generally only have random amino acid sequences. Interestingly, the two SFs, which are characterized by a structure composed of highly repetitive motifs, show several sharp far-IR characteristic absorption peaks. Moreover, some of these characteristic peaks (such as the peaks at 260 and 428 cm-1 in B. mori, and the peaks at 245 and 448 cm-1 in A. pernyi) are sensitive to conformational changes; hence, they can be directly used to monitor conformational transitions in SFs. Furthermore, since SF absorption bands clearly differ from those of globular proteins and different SFs even show distinct adsorption bands, far-IR spectroscopy can be applied to distinguish and determine the specific SF component within protein blends.

Ultrafast Interlayer Electron Transfer in Incommensurate Transition Metal Dichalcogenide Homobilayers.

Two-dimensional materials, such as graphene, transition metal dichalcogenides, and phosphorene, can be used to construct van der Waals multilayer structures. This approach has shown potentials to produce new materials that combine novel properties of the participating individual layers. One key requirement for effectively harnessing emergent properties of these materials is electronic connection of the involved atomic layers through efficient interlayer charge or energy transfer. Recently, ultrafast charge transfer on a time scale shorter than 100 fs has been observed in several van der Waals bilayer heterostructures formed by two different materials. However, information on the transfer between two atomic layers of the same type is rare. Because these homobilayers are essential elements in constructing multilayer structures with desired optoelectronic properties, efficient interlayer transfer is highly desired. Here we show that electron transfer between two monolayers of MoSe2 occurs on a picosecond time scale. Even faster transfer was observed in homobilayers of WS2 and WSe2. The samples were fabricated by manually stacking two exfoliated monolayer flakes. By adding a graphene layer as a fast carrier recombination channel for one of the two monolayers, the transfer of the photoexcited carriers from the populated to the drained monolayers was time-resolved by femtosecond transient absorption measurements. The observed efficient interlayer carrier transfer indicates that such homobilayers can be used in van der Waals multilayers to enhance their optical absorption without significantly compromising the interlayer transport performance. Our results also provide valuable information for understanding interlayer charge transfer in heterostructures.

Enabling Visible-Light-Driven Selective CO2 Reduction by Doping Quantum Dots: Trapping Electrons and Suppressing H2 Evolution.

Quantum dots (QDs), a class of promising candidates for harvesting visible light, generally exhibit low activity and selectivity towards photocatalytic CO2 reduction. Functionalizing QDs with metal complexes (or metal cations through ligands) is a widely used strategy for improving their catalytic activity; however, the resulting systems still suffer from low selectivity and stability in CO2 reduction. Herein, we report that doping CdS QDs with transition-metal sites can overcome these limitations and provide a system that enables highly selective photocatalytic reactions of CO2 with H2 O (100 % selectivity to CO and CH4 ), with excellent durability over 60 h. Doping Ni sites into the CdS lattice leads to effective trapping of photoexcited electrons at surface catalytic sites and substantial suppression of H2 evolution. The method reported here can be extended to various transition-metal sites, and offers new opportunities for exploring QD-based earth-abundant photocatalysts.

Isolation of Cu Atoms in Pd Lattice: Forming Highly Selective Sites for Photocatalytic Conversion of CO2 to CH4.

Photocatalytic conversion of CO2 to CH4, a carbon-neutral fuel, represents an appealing approach to remedy the current energy and environmental crisis; however, it suffers from the large production of CO and H2 by side reactions. The design of catalytic sites for CO2 adsorption and activation holds the key to address this grand challenge. In this Article, we develop highly selective sites for photocatalytic conversion of CO2 to CH4 by isolating Cu atoms in Pd lattice. According to our synchrotron-radiation characterizations and theoretical simulations, the isolation of Cu atoms in Pd lattice can play dual roles in the enhancement of CO2-to-CH4 conversion: (1) providing the paired Cu-Pd sites for the enhanced CO2 adsorption and the suppressed H2 evolution; and (2) elevating the d-band center of Cu sites for the improved CO2 activation. As a result, the Pd7Cu1-TiO2 photocatalyst achieves the high selectivity of 96% for CH4 production with a rate of 19.6 µmol gcat-1 h-1. This work provides fresh insights into the catalytic site design for selective photocatalytic CO2 conversion, and highlights the importance of catalyst lattice engineering at atomic precision to catalytic performance.

Defective Tungsten Oxide Hydrate Nanosheets for Boosting Aerobic Coupling of Amines: Synergistic Catalysis by Oxygen Vacancies and Brønsted Acid Sites.

Adsorption and activation of molecules on a surface holds the key to heterogeneous catalysis toward aerobic oxidative reactions. To achieve high catalytic activities, a catalyst surface should be rationally tailored to interact with both organic substrates and oxygen molecules. Here, a facile bottom-up approach to defective tungsten oxide hydrate (WO3 ·H2 O) nanosheets that contain both surface defects and lattice water is reported. The defective WO3 ·H2 O nanosheets exhibit excellent catalytic activity for aerobic coupling of amines to imines. The investigation indicates that the oxygen vacancies derived from surface defects supply coordinatively unsaturated sites to adsorb and activate oxygen molecules, producing superoxide radicals. More importantly, the Brønsted acid sites from lattice water can contribute to enhancing the adsorption and activation of alkaline amine molecules. The synergistic effect of oxygen vacancies and Brønsted acid sites eventually boosts the catalytic activity, which achieves a kinetic rate constant of 0.455 h-1 and a turnover frequency of 0.85 h-1 at 2 h, with the activation energy reduced to ≈35 kJ mol-1 . This work provides a different angle for metal oxide catalyst design by maneuvering subtle structural features, and highlights the importance of synergistic effects to heterogeneous catalysts.