Tunable Impedance of Cobalt Loaded Carbon for Wide-Range Electromagnetic Wave Absorption.

Impedance matching modulation of the electromagnetic wave (EMW) absorbers toward broad effective absorption bandwidth (EAB) is the ultimate aim in EMW attenuation applications. Here, a Joule heating strategy is reported for preparation of the Co-loaded carbon (Co/C) absorber with tunable impedance characteristics. Typically, the size of the Co can be regulated to range from single-atoms to clusters, and to nanocrystals. The varied sizes of the Co combined with different graphitization degrees of carbon can result in different relative input impedances and electromagnetic loss, leading to the tunable EMW absorption properties of the Co/C absorber. By meticulously coalescing the different prepared Co/C, the working frequency can be easily tuned, covering Ku, X, and C bands. Furthermore, the Co/C demonstrates a high EMW attenuation due to its unique dielectric loss capability and magnetic loss characteristics. The abundant interfaces of Co/C can also contribute to the enhanced interfacial polarization for improving EMW attenuation. This work demonstrates the importance of optimizing the metal and carbon interaction to the impedance matching toward wide EAB of the EMW absorbers.

Highly Stable Perovskite Oxides for Electrocatalytic Acidic NOx- Reduction Streamlining Ammonia Synthesis from Air.

Electrochemical nitrogen oxide ions reduction reaction (NOx-RR) shows great opportunity for ammonia production under ambient conditions. Yet, performing NOx-RR in strong acidic conditions remains challenging due to the corrosion effect on the catalyst and competing hydrogen evolution reactions. Here, we demonstrate a stable La1.5Sr0.5Ni0.5Fe0.5O4 perovskite oxide for the NOx-RR at pH 0, achieving a Faradaic efficiency for ammonia of approaching 100% at a current density of 2 A cm-2 in a H-type cell. At industrially relevant current density, the NOx-RR system shows stable cell voltage and Faradaic efficiency for >350 h in membrane electrode assembly (MEA) at pH 0. By integrating the catalyst in a stacked MEA with a series connection, we have successfully obtained a record-breaking 2.578 g h-1 NH3 production rate at 20 A. This catalyst's unique acid-operability streamlines downstream ammonia utilization for direct ammonium salt production and upstream integration with NOx sources. Techno-economic and lifecycle assessments reveal substantial economic advantages for this ammonia production strategy, even when coupled with a plasma-based NOx production system, presenting a sustainable complement to the conventional Haber-Bosch process.

Concentrated Formic Acid from CO2 Electrolysis for Directly Driving Fuel Cell.

The production of formic acid via electrochemical CO2 reduction may serve as a key link for the carbon cycle in the formic acid economy, yet its practical feasibility is largely limited by the quantity and concentration of the product. Here we demonstrate continuous electrochemical CO2 reduction for formic acid production at 2 M at an industrial-level current densities (i.e., 200 mA cm-2 ) for 300 h on membrane electrode assembly using scalable lattice-distorted bismuth catalysts. The optimized catalysts also enable a Faradaic efficiency for formate of 94.2 % and a highest partial formate current density of 1.16 A cm-2 , reaching a production rate of 21.7 mmol cm-2 h-1 . To assess the practicality of this system, we perform a comprehensive techno-economic analysis and life cycle assessment, showing that our approach can potentially substitute conventional methyl formate hydrolysis for industrial formic acid production. Furthermore, the resultant formic acid serves as direct fuel for air-breathing formic acid fuel cells, boasting a power density of 55 mW cm-2 and an exceptional thermal efficiency of 20.1 %.

Heterogeneous Single-Atom Photocatalysts: Fundamentals and Applications.

Single-atom photocatalysts have shown their compelling potential and arguably become the most active research direction in photocatalysis due to their fascinating strengths in enhancing light-harvesting, charge transfer dynamics, and surface reactions of a photocatalytic system. While numerous comprehensions about the single-atom photocatalysts have recently been amassed, advanced characterization techniques and vital theoretical studies are strengthening our understanding on these fascinating materials, allowing us to forecast their working mechanisms and applications in photocatalysis. In this review, we begin by describing the general background and definition of the single-atom photocatalysts. A brief discussion of the metal-support interactions on the single-atom photocatalysts is then provided. Thereafter, the current available characterization techniques for single-atom photocatalysts are summarized. After having some fundamental understanding on the single-atom photocatalysts, their advantages and applications in photocatalysis are discussed. Finally, we end this review with a look into the remaining challenges and future perspectives of single-atom photocatalysts. We anticipate that this review will provide some inspiration for the future discovery of the single-atom photocatalysts, manifestly stimulating the development in this emerging research area.

Phosphorus Tailors the d-Band Center of Copper Atomic Sites for Efficient CO2 Photoreduction under Visible-Light Irradiation.

Photoreduction of CO2 into solar fuels has received great interest, but suffers from low catalytic efficiency and poor selectivity. Herein, two single-Cu-atom catalysts with unique Cu configurations in phosphorus-doped carbon nitride (PCN), namely, Cu1 N3 @PCN and Cu1 P3 @PCN were fabricated via selective phosphidation, and tested in visible light-driven CO2 reduction by H2 O without sacrificial agents. Cu1 N3 @PCN was exclusively active for CO production with a rate of 49.8 µmolCO gcat -1 h-1 , outperforming most polymeric carbon nitride (C3 N4 ) based catalysts, while Cu1 P3 @PCN preferably yielded H2 . Experimental and theoretical analysis suggested that doping P in C3 N4 by replacing a corner C atom upshifted the d-band center of Cu in Cu1 N3 @PCN close to the Fermi level, which boosted the adsorption and activation of CO2 on Cu1 N3 , making Cu1 N3 @PCN efficiently convert CO2 to CO. In contrast, Cu1 P3 @PCN with a much lower Cu 3d electron energy exhibited negligible CO2 adsorption, thereby preferring H2 formation via photocatalytic H2 O splitting.

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.

Visible-Light-Driven Nitrogen Fixation Catalyzed by Bi5O7Br Nanostructures: Enhanced Performance by Oxygen Vacancies.

Photocatalytic nitrogen fixation represents a green alternative to the conventional Haber-Bosch process in the conversion of nitrogen to ammonia. In this study, a series of Bi5O7Br nanostructures were synthesized via a facile, low-temperature thermal treatment procedure, and their photocatalytic activity toward nitrogen fixation was evaluated and compared. Spectroscopic measurements showed that the tubular Bi5O7Br sample prepared at 40 °C (Bi5O7Br-40) exhibited the highest electron-transfer rate among the series, producing a large number of O2.- radicals and oxygen vacancies under visible-light photoirradiation and reaching a rate of photocatalytic nitrogen fixation of 12.72 mM·g-1·h-1 after 30 min of photoirradiation. The reaction dynamics was also monitored by in situ infrared measurements with a synchrotron radiation light source, where the transient difference between signals in the dark and under photoirradiation was analyzed and the reaction pathway of nitrogen fixation was identified. This was further supported by results from density functional theory calculations. The reaction energy of nitrogen fixation was quantitatively estimated and compared by building oxygen-enriched and anoxic models, where the change in the oxygen vacancy concentration was found to play a critical role in determining the nitrogen fixation performance. Results from this study suggest that Bi5O7Br with rich oxygen vacancies can be used as a high-performance photocatalyst for nitrogen fixation.

A Blinking Mesoporous TiO2-x Composed of Nanosized Anatase with Unusually Long-Lived Trapped Charge Carriers.

A mesoporous TiO2-x material comprised of small, crystalline, vacancy-rich anatase nanoparticles (NPs) shows unique optical, thermal, and electronic properties. It is synthesized using polymer-derived mesoporous carbon (PDMC) as a template. The PDMC pores serve as physical barriers during the condensation and pyrolysis of a titania precursor, preventing the titania NPs from growing beyond 10 nm in size. Unlike most titania nanomaterials, during pyrolysis the NPs undergo no transition from the anatase to rutile phase and they become catalytically active reduced TiO2-x . When exposed to a slow electron beam, the NPs exhibit a charge/discharge behavior, lighting up and fading away for an average period of 15 s for an extended period of time. The NPs also show a 50 nm red-shift in their UV/Vis absorption and long-lived charge carriers (electrons and holes) at room temperature in the dark, even long after UV irradiation. The NPs as photocatalysts show a good activity for CO2 reduction.

Enhanced photocatalytic CO2-reduction activity of anatase TiO2 by coexposed {001} and {101} facets.

Control of TiO2 crystal facets has attracted enormous interest due to the fascinating shape-dependent photocatalytic activity of this material. In this work, the effect of the ratio of {001} and {101} facets on the photocatalytic CO2-reduction performance of anatase TiO2 is reported. A new "surface heterojunction" concept is proposed on the basis of the density functional theory (DFT) calculations to explain the difference in the photocatalytic activity of TiO2 with coexposed {001} and {101} facets.

Enhanced visible-light photocatalytic activity of plasmonic Ag and graphene co-modified Bi2WO6 nanosheets.

Photocatalytic degradation of pollutants in water has received much attention due to increasing environmental problems. In this study, a visible-light-driven plasmonic silver-graphene-bismuth tungsten (Ag-G-Bi2WO6) composite photocatalyst was prepared. Firstly, the graphite oxide (GO)-Bi2WO6 composite was prepared using a hydrothermal process, followed by a chemical reduction process using ethyl glycol (EG) as the reducing agent to form the G-Bi2WO6 composite. Then, Ag nanoparticles (NPs) were loaded onto the G-Bi2WO6 composite using a simple photochemical reduction process under xenon lamp irradiation to form the Ag-G-Bi2WO6 composite. The prepared samples were characterized using X-ray diffraction, transmission electron microscopy, nitrogen adsorption-desorption isotherm, UV-visible diffuse reflectance spectroscopy and electrochemical impedance spectroscopy. The photocatalytic activities of the prepared samples were evaluated by the photocatalytic degradation of rhodamine B (RhB) aqueous solution at ambient temperature under visible-light irradiation. The results showed that the photocatalytic activity of Bi2WO6 was significantly enhanced by the loading of Ag and graphene. The high photocatalytic activity is attributed predominantly to the hybridization of the surface plasmonic resonance (SPR) effect of Ag NPs and the specific electronics effect of graphene on the Bi2WO6 surface, thus enhancing the generation and separation of photogenerated charge carriers of Bi2WO6. Meanwhile, the excellent adsorption capacity of graphene also contributes to the enhancement of photocatalytic activity. This work highlights the design and preparation of new photocatalysts using plasmonic Ag and graphene as cocatalyst.

Full-Space Electric Field in Mo-Decorated Zn2In2S5 Polarization Photocatalyst for Oriented Charge Flow and Efficient Hydrogen Production.

Integration of photocatalytic hydrogen (H2) evolution with oxidative organic synthesis presents a highly attractive strategy for the simultaneous production of clean H2 fuel and high-value chemicals. However, the sluggish dynamics of photogenerated charge carriers across the photocatalysts result in low photoconversion efficiency, hindering the wide applications of such a technology. Herein, this work overcomes this limitation by inducing the full-space electric field via charge polarization engineering on a Mo cluster-decorated Zn2In2S5 (Mo-Zn2In2S5) photocatalyst. Specifically, this full-space electric field arises from a cascade of the bulk electric field (BEF) and local surface electric field (LSEF), triggering the oriented migration of photogenerated electrons from [Zn-S] regions to [In-S] regions and eventually to Mo cluster sites, ensuring efficient separation of bulk and surface charge carriers. Moreover, the surface Mo clusters induce a tip enhancement effect to optimize charge transfer behavior by augmenting electrons and proton concentration around the active sites on the basal plane of Zn2In2S5. Notably, the optimized Mo1.5-Zn2In2S5 catalyst achieves exceptional H2 and benzaldehyde production rates of 34.35 and 45.31 mmol gcat -1 h-1, respectively, outperforming pristine ZnIn2S4 by 3.83- and 4.15-fold. These findings mark a significant stride in steering charge flow for enhanced photocatalytic performance.

Spectroscopic visualization of reversible hydrogen spillover between palladium and metal-organic frameworks toward catalytic semihydrogenation.

Hydrogen spillover widely occurs in a variety of hydrogen-involved chemical and physical processes. Recently, metal-organic frameworks have been extensively explored for their integration with noble metals toward various hydrogen-related applications, however, the hydrogen spillover in metal/MOF composite structures remains largely elusive given the challenges of collecting direct evidence due to system complexity. Here we show an elaborate strategy of modular signal amplification to decouple the behavior of hydrogen spillover in each functional regime, enabling spectroscopic visualization for interfacial dynamic processes. Remarkably, we successfully depict a full picture for dynamic replenishment of surface hydrogen atoms under interfacial hydrogen spillover by quick-scanning extended X-ray absorption fine structure, in situ surface-enhanced Raman spectroscopy and ab initio molecular dynamics calculation. With interfacial hydrogen spillover, Pd/ZIF-8 catalyst shows unique alkyne semihydrogenation activity and selectivity for alkynes molecules. The methodology demonstrated in this study also provides a basis for further exploration of interfacial species migration.

Enhanced photocatalytic performance of direct Z-scheme g-C3N4-TiO2 photocatalysts for the decomposition of formaldehyde in air.

Formaldehyde (HCHO) is a major indoor pollutant and long-term exposure to HCHO may cause health problems such as nasal tumors and skin irritation. Photocatalytic oxidation is considered as the most promising strategy for the decomposition of HCHO. Herein, for the first time, a direct g-C3N4-TiO2 Z-scheme photocatalyst without an electron mediator was prepared by a facile calcination route utilizing affordable P25 and urea as the feedstocks. Photocatalytic activities of the as-prepared samples were evaluated by the photocatalytic oxidation decomposition of HCHO in air. It was shown that the photocatalytic activity of the prepared Z-scheme photocatalysts was highly dependent on the g-C3N4 content. At the optimal g-C3N4 content (sample U100 in this study), the apparent reaction rate constant was 7.36 × 10(-2) min(-1) for HCHO decomposition, which exceeded that of pure P25 (3.53 × 10(-2) min(-1)) by a factor of 2.1. The enhanced photocatalytic activity could be ascribed to the formation of a g-C3N4-TiO2 Z-scheme photocatalyst, which results in the efficient space separation of photo-induced charge carriers. Considering the ease of the preparation method, this work will provide new insights into the design of high-performance Z-scheme photocatalysts for indoor air purification.

Tunable Interfacial Charge Transfer in a 2D-2D Composite for Efficient Visible-Light-Driven CO2 Conversion.

Photocatalytic CO2 conversion for hydrocarbon fuel production has been known as one of the most promising strategies for achieving carbon neutrality. Yet, its conversion efficiency remains unsatisfactory mainly due to its severe charge-transfer resistance and slow charge kinetics. Herein, a tunable interfacial charge transfer on an oxygen-vacancies-modified bismuth molybdate nanoflower assembled by 2D nanosheets (BMOVs) and 2D bismuthene composite (Bi/BMOVs) is demonstrated for photocatalytic CO2 conversion. Specifically, the meticulous design of the Ohmic contact formed between BMOVs and bismuthene can allow the modulation of the interfacial charge-transfer resistance. According to density functional theory (DFT) simulations, it is ascertained that such exceptional charge kinetics is attributed to the tunable built-in electric field (IEF) of the Ohmic contact. As such, the photocatalytic CO2 reduction performance of the optimized Bi/BMOVs (CO and CH4 productions rate of 169.93 and 4.65 µmol g-1 h-1 , respectively) is ca. 10 times higher than that of the pristine BMO (CO and CH4 production rates of 16.06 and 0.51 µmol g-1 h-1 , respectively). The tunable interfacial resistance of the Ohmic contact reported in this work can shed some important light on the design of highly efficient photocatalysts for both energy and environmental applications.

Self-activated superhydrophilic green ZnIn2S4 realizing solar-driven overall water splitting: close-to-unity stability for a full daytime.

Engineering an efficient semiconductor to sustainably produce green hydrogen via solar-driven water splitting is one of the cutting-edge strategies for carbon-neutral energy ecosystem. Herein, a superhydrophilic green hollow ZnIn2S4 (gZIS) was fabricated to realize unassisted photocatalytic overall water splitting. The hollow hierarchical framework benefits exposure of intrinsically active facets and activates inert basal planes. The superhydrophilic nature of gZIS promotes intense surface water molecule interactions. The presence of vacancies within gZIS facilitates photon energy utilization and charge transfer. Systematic theoretical computations signify the defect-induced charge redistribution of gZIS enhancing water activation and reducing surface kinetic barriers. Ultimately, the gZIS could drive photocatalytic pure water splitting by retaining close-to-unity stability for a full daytime reaction with performance comparable to other complex sulfide-based materials. This work reports a self-activated, single-component cocatalyst-free gZIS with great exploration value, potentially providing a state-of-the-art design and innovative aperture for efficient solar-driven hydrogen production to achieve carbon-neutrality.

Active Site Engineering on Plasmonic Nanostructures for Efficient Photocatalysis.

Plasmonic nanostructures have shown immense potential in photocatalysis because of their distinct photochemical properties associated with tunable photoresponses and strong light-matter interactions. The introduction of highly active sites is essential to fully exploit the potential of plasmonic nanostructures in photocatalysis, considering the inferior intrinsic activities of typical plasmonic metals. This review focuses on active site-engineered plasmonic nanostructures with enhanced photocatalytic performance, wherein the active sites are classified into four types (i.e., metallic sites, defect sites, ligand-grafted sites, and interface sites). The synergy between active sites and plasmonic nanostructures in photocatalysis is discussed in detail after briefly introducing the material synthesis and characterization methods. Active sites can promote the coupling of solar energy harvested by plasmonic metal to catalytic reactions in the form of local electromagnetic fields, hot carriers, and photothermal heating. Moreover, efficient energy coupling potentially regulates the reaction pathway by facilitating the excited state formation of reactants, changing the status of active sites, and creating additional active sites using photoexcited plasmonic metals. Afterward, the application of active site-engineered plasmonic nanostructures in emerging photocatalytic reactions is summarized. Finally, a summary and perspective of the existing challenges and future opportunities are presented. This review aims to deliver some insights into plasmonic photocatalysis from the perspective of active sites, expediting the discovery of high-performance plasmonic photocatalysts.

Near-infrared-featured broadband CO2 reduction with water to hydrocarbons by surface plasmon.

Imitating the natural photosynthesis to synthesize hydrocarbon fuels represents a viable strategy for solar-to-chemical energy conversion, where utilizing low-energy photons, especially near-infrared photons, has been the ultimate yet challenging aim to further improving conversion efficiency. Plasmonic metals have proven their ability in absorbing low-energy photons, however, it remains an obstacle in effectively coupling this energy into reactant molecules. Here we report the broadband plasmon-induced CO2 reduction reaction with water, which achieves a CH4 production rate of 0.55 mmol g-1 h-1 with 100% selectivity to hydrocarbon products under 400 mW cm-2 full-spectrum light illumination and an apparent quantum efficiency of 0.38% at 800 nm illumination. We find that the enhanced local electric field plays an irreplaceable role in efficient multiphoton absorption and selective energy transfer for such an excellent light-driven catalytic performance. This work paves the way to the technique for low-energy photon utilization.

Sustainable methane utilization technology via photocatalytic halogenation with alkali halides.

Methyl halides are versatile platform molecules, which have been widely adopted as precursors for producing value-added chemicals and fuels. Despite their high importance, the green and economical synthesis of the methyl halides remains challenging. Here we demonstrate sustainable and efficient photocatalytic methane halogenation for methyl halide production over copper-doped titania using alkali halides as a widely available and noncorrosive halogenation agent. This approach affords a methyl halide production rate of up to 0.61 mmol h-1 m-2 for chloromethane or 1.08 mmol h-1 m-2 for bromomethane with a stability of 28 h, which are further proven transformable to methanol and pharmaceutical intermediates. Furthermore, we demonstrate that such a reaction can also operate solely using seawater and methane as resources, showing its high practicability as general technology for offshore methane exploitation. This work opens an avenue for the sustainable utilization of methane from various resources and toward designated applications.

In situ resource utilization of lunar soil for highly efficient extraterrestrial fuel and oxygen supply.

Building up a lunar settlement is the ultimate aim of lunar exploitation. Yet, limited fuel and oxygen supplies restrict human survival on the Moon. Herein, we demonstrate the in situ resource utilization of lunar soil for extraterrestrial fuel and oxygen production, which may power up our solely natural satellite and supply respiratory gas. Specifically, the lunar soil is loaded with Cu species and employed for electrocatalytic CO2 conversion, demonstrating significant production of methane. In addition, the selected component in lunar soil (i.e. MgSiO3) loaded with Cu can reach a CH4 Faradaic efficiency of 72.05% with a CH4 production rate of 0.8 mL/min at 600 mA/cm2. Simultaneously, an O2 production rate of 2.3 mL/min can be achieved. Furthermore, we demonstrate that our developed process starting from catalyst preparation to electrocatalytic CO2 conversion is so accessible that it can be operated in an unmmaned manner via a robotic system. Such a highly efficient extraterrestrial fuel and oxygen production system is expected to push forward the development of mankind's civilization toward an extraterrestrial settlement.