Stable CO2reduction under natural air on Ni-Sn hydroxide photocatalyst with dynamic renewable oxygen vacancies.

Advanced photocatalysts are highly desired to activate the photocatalytic CO2reduction reaction (CO2RR) with low concentration. Herein, the NiSn(OH)6with rich surface lattice hydroxyls was synthesized to boost the activity directly under the natural air. Results showed that terminal Ni-OH could serve as donors to feed protons and generate oxygen vacancies (VO), thus beneficial to convert the activated CO2(HCO3-) mainly into CO (5.60µmol g-1) in the atmosphere. It was flexible and widely applicable for a stable CO2RR from high pure to air level free of additionally adding H2O reactant, and higher than the traditional gas-liquid-solid (1.58µmol g-1) and gas-solid (4.07µmol g-1) reaction system both using high pure CO2and plenty of H2O. The strong hydrophilia by the rich surface hydroxyls allowed robust H2O molecule adsorption and dissociation at VOsites to achieve the Ni-OH regeneration, leading to a stable CO yield (11.61µmol g-1) with the enriched renewable VOregardless of the poor CO2and H2O in air. This work opens up new possibilities for the practical application of natural photosynthesis.

Composite interfaces of g-C3N4 fragments loaded on a Cu substrate for CO2 reduction.

Designing an electrocatalyst with high efficiency and product selectivity is always crucial for an electrocatalytic CO2 reduction reaction (CO2RR). Inspired by the great progress of two-dimensional (2D) nanomaterials growing on Cu surfaces and their promising CO2RR catalytic efficiencies at their interfaces, the unique performance of Cu-based 2D materials as high-efficiency and low-cost CO2RR electrocatalysts has attracted extensive attention. Herein, based on density functional theory (DFT) calculations, we proposed a composite structure of graphitic carbon nitride (g-C3N4) fragments loaded on a Cu surface to explore the CO2RR catalytic property of the interface between g-C3N4 and the Cu surface. Three composite interfaces of C3N4/Cu(111), C3N4/Cu(110) and C3N4/Cu(100) have been studied by considering the reaction sites of vertex nitrogen atoms, edge nitrogen atoms and the nearby Cu atoms. It was found that the C3N4/Cu interfaces where nitrogen atoms contact the Cu substrate present competitive CO2RR activity. Among them, C3N4/Cu(111)-N3 exhibited a better activity for CH3OH production, with a low overpotential of 0.38 V. For HCOOH and CH4 production, C3N4/Cu(111)-Cu and C3N4/Cu(100)-N1 have overpotentials of 0.26 V and 0.44 V. The electronic analysis indicates the electron transfer from the Cu substrate to the g-C3N4 fragment and mainly accumulates on the nitrogen atoms of the interface. Such charge accumulation can activate the adsorbed CO bond of CO2 and lead to lower energetic barriers of CO2RR. DFT calculations indicate that the boundary nitrogen sites reduced the energy barrier of *CHO, which is crucial for CO2RR, compared with that of the pristine Cu surface. Our study explores a new Cu-based electrocatalyst and indicates that the C3N4/Cu interface can enhance the activities and selectivity of CO2RR and open a new strategy to design high-efficiency electrocatalysts for CO2RR.

ZnO-Au@ZIF-8 core-shell nanorod arrays for ppb-level NO2 detection.

ZnO-Au@ZIF-8 core-shell heterostructures were prepared by ZIF-8 encapsulation of sacrificial ZnO-Au nanorods. Because of the catalytic activity of the Au nanoparticles and the sieving effects of the ZIF-8, the ZnO-Au@ZIF-8 heterostructures showed an outstanding response of 1.8 to 5 ppb NO2, and exhibited higher selectivity, stability, anti-humidity and fast response and recovery properties. The combination of the gas-selective catalytic activity of noble metals with the MOF filter used in this work can be easily extended to synthesize other types of MOS@MOF sensors, opening a new avenue for the detection of hazardous gases.

A 2D-0D-2D Sandwich Heterostructure toward High-Performance Room-Temperature Gas Sensing.

The construction of two-dimensional (2D) van der Waals (vdW) heterostructures over black phosphorus (BP) has been attracting significant attention to better utilize its inherent properties. The sandwich of zero-dimensional (0D) noble metals within BP-based vdW heterostructures can provide efficient catalytic channels, modulating their surface redox potentials and therefore inducing versatile functionalities. Herein, we realize a 2D WS2-Au-BP heterostructure, in which Au nanoparticles are connected between BP and WS2 via ionic bonds. The ultralow conduction band minimum position, the reduced adsorption energies of O2, and the increased dissociation barrier energy of O2- into 2O contribute greatly to improving the long-term stability of BP in the air. The formation of heterostructures can reduce the potential barrier energy in target gas molecules, thus enhancing the absorption energy and charge transfer. Taking the paramagnetic NO2 gas molecules as a representative, a stable response magnitude of 2.11 to 100 ppb NO2 is achieved for 80 days, which is far larger than the initial responses of most BP-based materials. A practical gas sensing system is also developed to demonstrate its real-world implementation. This work provides a promising demonstration of 0D noble metal within 2D BP-based vdW heterostructure for simultaneously improving the long-term stability and room-temperature reversible gas sensing.

Enhance Hydrogen Evolution Reaction Performance via Double-Stacked Edges of Black Phosphorene.

Based on the density functional theory (DFT) calculations, we explored the structures and HER catalytic properties of reconstructed and double-stacked black phosphorene (BP) edges. Ten bilayer BP edges were constructed by the double stacking of three typical monolayer edges, i.e., zigzag (ZZ) edge, armchair (AC) edge, skewed diagonal (SD) edge, and their reconstructed derivatives with their layer's configurations, edge deformations and thermodynamic stabilities were discussed. Based on these edges, five chemical sites on four bilayer BP edges were selected to be promising candidates for a HER catalyst, which present higher HER activities than that of Pt(111). Besides, among these four edges, two edges have even lower energetic barriers for the Tafel reaction. Compared with the monolayer edges, these selected bilayer BP edges confirm the remarkable enhancement of the HER catalytic properties, which can be attributed to their unique edge structures and the enhanced electronic densities after the hydrogen adsorptions. Finally, the thermostability of these edges at room temperature has also been proved by the DFT-MD simulations. This theoretic study deepens our fundamental understanding of the double-stacked edge structures of the BP and provides a new way for the rational design of highly efficient and noble-metal-free HER catalysts.

Realizing the Ultralow Lattice Thermal Conductivity of Cu3SbSe4 Compound via Sulfur Alloying Effect.

Cu3SbSe4 is a potential p-type thermoelectric material, distinguished by its earth-abundant, inexpensive, innocuous, and environmentally friendly components. Nonetheless, the thermoelectric performance is poor and remains subpar. Herein, the electrical and thermal transport properties of Cu3SbSe4 were synergistically optimized by S alloying. Firstly, S alloying widened the band gap, effectively alleviating the bipolar effect. Additionally, the substitution of S in the lattice significantly increased the carrier effective mass, leading to a large Seebeck coefficient of ~730 µVK-1. Moreover, S alloying yielded point defect and Umklapp scattering to significantly depress the lattice thermal conductivity, and thus brought about an ultralow κlat ~0.50 Wm-1K-1 at 673 K in the solid solution. Consequently, multiple effects induced by S alloying enhanced the thermoelectric performance of the Cu3SbSe4-Cu3SbS4 solid solution, resulting in a maximum ZT value of ~0.72 at 673 K for the Cu3SbSe2.8S1.2 sample, which was ~44% higher than that of pristine Cu3SbSe4. This work offers direction on improving the comprehensive TE in solid solutions via elemental alloying.

High Detectivity of PbS Films Deposited on Quartz Substrates: The Role of Enhanced Photogenerated Carrier Separation.

PbS films grown on quartz substrates by the chemical bath deposition method were annealed in an O2 atmosphere to investigate the role of oxygen in the sensitization process at different annealing temperatures. The average grain size of the PbS films gradually increased as the annealing temperature increased from 400 °C to 700 °C. At an annealing temperature of 650 °C, the photoresponsivity and detectivity reached 1.67 A W-1 and 1.22 × 1010 cm Hz1/2 W-1, respectively. The role of oxides in the sensitization process was analyzed in combination with X-ray diffraction and scanning electron microscopy results, and a three-dimensional network model of the sensitization mechanism of PbS films was proposed. During the annealing process, O functioned as a p-type impurity, forming p+-type PbS layers with high hole concentrations on the surface and between the PbS grains. As annealing proceeds, the p+-type PbS layers at the grain boundaries interconnect to form a three-dimensional network structure of hole transport channels, while the unoxidized p-type PbS layers act as electron transport channels. Under bias, photogenerated electron-hole pairs were efficiently separated by the formed p+-p charge separation junction, thereby reducing electron-hole recombination and facilitating a higher infrared response.

Exploring the gas-sensing properties of MOF-derived TiN@CuO as a hydrogen sulfide sensor.

In an effort to develop a long-lasting gas sensor, this article presents titanium nitride (TiN) as a potential substitute sensitive material in conjunction with (copper(II) benzene-1,3,5-tricarboxylate) Cu-BTC-derived CuO. The work focused on the gas-sensing characteristics of TiN/CuO nanoparticles in detecting H2S gas at various temperatures and concentrations. XRD, XPS, and SEM were utilized to analyze the composites with varied Cu molar ratios. The responses of TiN/CuO-2 nanoparticles to 50 and 100 ppm H2S gas at 50 °C and 250 °C are 34.8 and 60.0, respectively. The related sensor had high selectivity and stability towards H2S, and the response of TiN/CuO-2 is still 2.5-5 ppm H2S. The gas-sensing properties as well as the mechanism are fully explained in this study. TiN/CuO might be a choice for the detection of H2S gas, opening up new avenues for applications in industries, medical facilities, and homes.

Multifunctional Au/Hydroxide Interface toward Enhanced C-C Coupling for Solar-Driven CO2 Reduction into C2H6.

The high-grade C2+ products from CO2 photoreduction are limited by the kinetic bottleneck. Herein, a multifunctional Au/hydroxide interface was put forward to improve the C-C coupling. As a prototype, the synthesized Au/ZnSn(OH)6 tuned the CO generation and afforded about 50% electrons toward C2H6 selectivity. The prominent enhancement resulted from the following effects: (1) strong metal-support electronic interactions built an electric field at the interface of ZnSn(OH)6 nearby the Au nanoparticles, leading to fast transfer of electrons for the C-H and C-C bonding reactions. (2) The surface solid-state Sn-OH and Zn-OH lattice hydroxyls served as donors to feed rich H+ and oxygen vacancies (OVs) via hole-induced oxidation for the boosted C2H6 formation. (3) The synergetic OVs and Au sites allowed efficient e-/H+ to boost *CO hydrogenation toward *CH3 and *CH3*CH3 formation into the C2H6 product.

Quasi-one-dimensional phosphorene nanoribbons grown on silicon by space-confined chemical vapor transport.

Phosphorene nanoribbons (PNRs) combine the flexibility of one-dimensional (1D) nanomaterials with the large specific surface area and the edge and electron confinement effects of two-dimensional (2D) nanomaterials. In spite of the substantial advances in bulk black phosphorus (BP) manufacturing, achieving PNRs without degradation is still a big challenge. In this work, we present a strategy for the space-confined chemical vapor transport synthesis of quasi-one-dimensional surface-passivated monocrystalline PNRs on a silicon substrate. The growth mechanism of the PNRs is proposed by combining experimental results and DFT calculations, indicating that the P4 molecules can break, restructure, and epitaxially nucleate on the surface of the Au3SnP7 catalyst, and finally prefer to grow along the zigzag (ZZ) direction to form PNRs. The low gas flow rate and an appropriate phosphorus molecule concentration allow the growth of PNRs with structural integrity, which can be regulated by the amount of red phosphorus and the confined space.

CuO-decorated MOF derived ZnO polyhedral nanostructures for exceptional H2S gas detection.

Considering that H2S is a hazardous gas that poses a significant risk to people's lives, research into H2S gas sensors has garnered a lot of interest. This work reports a CuO/ZnO multifaceted nanostructures(NS) created by heat treating Cu2+/ZIF-8 impregnation precursors, and their microstructure and gas sensing characteristics were examined using various characterization techniques (XRD, XPS, SEM, TEM, and BET). The as-prepared hollow CuO/ZnO multifunctional nanostructures had a high gas response value (425@50 ppm H2S gas), quick response and recovery times (57/191s @20 ppm), a low limit of detection (1.6@500 ppb H2S), good humidity resistance and highly selective towards H2S gas. The hollow CuO/ZnO multifaceted nanostructures possessed enhanced gas sensing capabilities which may be related to their porous hollow nanostructures, the manufactured p-CuO/n-ZnO heterojunctions, and the spillover effect between CuO and H2S.

Metal-organic frameworks-derived In2O3/ZnO porous hollow nanocages for highly sensitive H2S gas sensor.

The detection of hydrogen sulfide (H2S) is critical because of its potential harm and widespread presence in the oil and gas sectors. The zeolitic imidazolate framework-8 (ZIF-8) derived ZnO nanostructures manufactured as gas sensors have exceptional sensitivity and selectivity for H2S gas. In/Zn-ZIF-8 template material was synthesized by a simple one-step co-precipitation method followed by thermal annealing in air. The heat treatment resulted in In2O3/ZnO nanostructures with mixed heterostructures. The crystal structure (XRD), morphology (SEM/TEM), chemical state (XPS), surface area (BET), etc were investigated to ascertain the nature of the as-prepared material. SEM imagery revealed that the as-prepared In2O3/ZnO sensitive material had a microstructure of porous hollow nanocages with an average particle size of about 200 nm, which is beneficial to the diffusion and adsorption of gas molecules. The gas sensing performance test results of the In2O3/ZnO hollow nanocages show that their response to H2S gas is significantly improved 67.5 @50 ppm H2S (about 11 times that of pure ZnO nanocages) at an optimal temperature of 200 °C, better selectivity, lower theoretical detection limit and good linearity between gas concentration and response values. The enhanced gas sensing feat to H2S gas is mainly attributed to the formation of n-n heterojunction and the wide surface area of the newly formed In2O3/ZnO porous hollow nanocages.

Facile fabrication of nanoflower-like WO3/WS2 heterojunction for highly sensitive NO2 detection at room temperature.

Realizing efficient detection of ultra-low concentrations of hazardous gases contributes to air pollution monitoring, ecosystem and human health protection. Herein, we firstly fabricated the nanoflower-like WO3/WS2 composites by a facile process to highly sensitively detect NO2 at room temperature. The WO3 content in the WO3/WS2 composites can be adjusted by altering the calcination temperature, and the WO3 nanoparticles disperse uniformly on the WS2 surface, forming the WO3/WS2 heterojunction. The room-temperature responses of WO3/WS2 composites gradually climb with the NO2 concentration increasing from 0.005 to 5 ppm, and the WW-280 and WW-300 composites possess the optimal gas sensitivity when the NO2 concentrations are lower and higher than 100 ppb, respectively. In particular, the two WO3/WS2 composites present the limitation of detection (LOD) of ≤ 5 ppb, and they exhibit the excellent selectivity, good reproducibility and long-term stability towards NO2. A possible gas sensing mechanism was also proposed from the point of views of gas adsorption, redox reactions and electron transfer. The appropriate WO3 content and molar ratio of hexagonal to monoclinic WO3, and the formation of WO3/WS2 p-n heterojunction can contribute to the high sensitivity of WO3/WS2 composite to various concentrations of NO2. This work offers a promising gas sensing material for room-temperature detection to low concentrations of NO2.

Atomic Level Defect Structure Engineering for Unusually High Average Thermoelectric Figure of Merit in n-Type PbSe Rivalling PbTe.

Realizing high average thermoelectric figure of merit (ZTave ) and power factor (PFave ) has been the utmost task in thermoelectrics. Here the new strategy to independently improve constituent factors in ZT is reported, giving exceptionally high ZTave and PFave in n-type PbSe. The nonstoichiometric, alloyed composition and resulting defect structures in new Pb1+ x Se0.8 Te0.2 (x = 0-0.125) system is key to this achievement. First, incorporating excess Pb unusually increases carrier mobility (µH ) and concentration (nH ) simultaneously in contrast to the general physics rule, thereby raising electrical conductivity (σ). Second, modifying charge scattering mechanism by the authors' synthesis process boosts a magnitude of Seebeck coefficient (S) above theoretical expectations. Detouring the innate inverse proportionality between nH and µH ; and σ and S enables independent control over them and change the typical trend of PF to temperature, giving remarkably high PFave ≈20 µW cm-1 K-2 from 300 to 823 K. The dual incorporation of Te and excess Pb generates unusual antisite Pb at the anionic site and displaced Pb from the ideal position, consequently suppressing lattice thermal conductivity. The best composition exhibits a ZTave of ≈1.2 from 400 to 823 K, one of the highest reported for all n-type PbQ (Q = chalcogens) materials.

Efficient detection of hazardous H2S gas using multifaceted Co3O4/ZnO hollow nanostructures.

The rapid increases in environmental hazardous gases have laid dangerous effects on human health. The detection of such pollutants gases is mandatory using various optimal techniques. In this paper, porous multifaceted Co3O4/ZnO nanostructures are synthesized by pyrolyzing sacrificial template of core-shell double zeolitic imidazolate frameworks (ZIFs) for gas sensing applications. The fabricated exhibit superior gas sensor response, high selectivity, fast response/recovery times, and remarkable stability and sensitivity to H2S gas. In particular, the multifaceted Co3O4/ZnO nanostructures show a maximum response of 147 at 100 ppm of H2S under optimum conditions. The remarkable gas sensing performances are mainly ascribed to high porosity, wide surface area multifaceted nanostructures, presence of heterojunctions and catalytic activity of ZnO and Co3O4, which are beneficial for H2S gas sensors industry.

Enhanced NO2 gas-sensing performance by core-shell SnO2/ZIF-8 nanospheres.

Timely detection of harmful, poisonous and air pollutant gases is of vital importance to the protection of human beings from exposure to rigorous gases. The development of gas-sensing devices based on sphere-like porous SnO2/ZIF-8 nanocomposites is required to overcome this challenge. Nanostructures with high surface area, more porosity and hollow interior provide plenty of active cites for high responses in metal oxide gas sensors. The engineered gas sensors have excellent sensing sensitivity (164), rapid response and recovery times (60, 45 s), and favorable selectivity for NO2 gases under 300 °C. Consequently, NO2 gas sensors based on core-shell SnO2/ZIF-8 nanospheres are regarded viable capacity industrial applicants.

Theoretical Study on P-coordinated Metal Atoms Embedded in Arsenene for the Conversion of Nitrogen to Ammonia.

The conversion of gaseous N2 to ammonia under mild conditions by artificial methods has become one of the hot topics and challenges in the field of energy research today. Accordingly, based on density function theory calculations, we comprehensively explored the d-block of metal atoms (Ti, V, Cr, Mn, Fe, Co, Ni, Nb, Mo, Ru, Rh, W, and Pt) embedded in arsenene (Ars) for different transition systems of phosphorus (P) coordination as potential electrocatalysts for N2 reduction reaction (NRR). By adopting a "two-step" strategy with stringent NRR catalyst screening criteria, we eventually selected Nb@P3-Ars as a research object for a further in-depth NRR mechanism study. Our results show that Nb@P3-Ars not only maintains the thermodynamic stability at mild temperatures but also dominates the competition with the hydrogen evolution reaction when used as the electrochemical NRR (e-NRR) catalyst. In particular, while the NRR process occurs by the distal mechanism, Nb@P3-Ars has a low overpotential (0.36 V), which facilitates the efficient reduction of N2. Therefore, this work predicts the possibility of Nb@P3-Ars as an e-NRR catalyst for reducing N2 from a theoretical perspective and provides significant insights and theoretical guidance for future experimental research.

Single atom-doped arsenene as electrocatalyst for reducing nitrogen to ammonia: a DFT study.

Due to the wide application of NH3 in the energy and chemical industry, the rational design of a highly efficient and low-cost electrocatalyst for nitrogen fixation at moderate conditions is highly desirable to meet the increasing demand for sustainable energy production in the modern society. Herein, we have systematically studied the catalytic performance of transition metal (TM) atom (i.e., V, Cr, Fe, Co, Cu, Ru, Pd, Ag, Pt, Au)-doped arsenene nanosheet, a new two-dimensional (2D) nanomaterial in VA group, as a heterogeneous catalyst for nitrogen reduction reaction (NRR). By density functional theory (DFT) calculation and systematic theoretical screening, our study predicts that the systems of V-, Fe-, Co- and Ru-doped arsenene have promising potentials as NRR electrocatalysts with high-loading TM and highly stable adsorption of N2 molecule. Particularly, the V-doped system exhibits two feasible configurations for N2 adsorption and an ultralow overpotential (0.10 V) via the enzymatic pathway, which is very competitive among similar reported electrocatalysts. This theoretical study not only extends the electrocatalyst family for nitrogen fixation, but also further deepens our physical insights into catalytic improvement, which can be expected to guide the rational design of novel NRR catalysts.

Solution-Processed Sb2Se3 on TiO2 Thin Films Toward Oxidation- and Moisture-Resistant, Self-Powered Photodetectors.

Semiconductor-sensitized TiO2 thin films with long-term air stability are attractive for optoelectronic devices and applications. Herein, we demonstrate the potential of the TiO2 thin film (∼800 nm in thickness) sensitized with a Sb2Se3 layer (∼350 nm) grown from solution spin coating and processed by annealing recrystallization at 300 °C for high-performance optical detection. The type-II band alignment, p-Sb2Se3/n-TiO2 heterojunction, and narrow band gap of Sb2Se3 (∼1.25 eV) endow the film photodetector with a large photocurrent, high switching stability and on/off ratio (>103), and fast response speeds (<20 ms) under the broadband visible-near-infrared irradiation in a zero-bias self-powered photovoltaic mode. In particular, the photodetector shows notable resistance to oxidation and moisture for long-term operation, which is linked to the modest surface oxidation (Sb-O) of Sb2Se3, as verified by X-ray photoelectron spectroscopy. The first-principles calculations show that a low and medium concentration of oxygen substitution for Se (OSe) and oxygen interstitial (Oi) with negative formation energies can lead to such a moderate surface oxidation but do not generate impurity states or just introduce a shallow-level acceptor state in the electronic structures of Sb2Se3 without degrading its optoelectronic performance. Our theoretical results offer a rational explanation for the air-stable and oxidation/moisture-resistant characteristics in moderately oxidized Sb2Se3 and may shed light on the surface oxidation-property relationship studies of other nonoxide semiconductor-sensitized devices.

Construction of hierarchical trimetallic organic framework leaf-like nanostructures derived from carbon nanotubes for gas-sensing applications.

Unique trimetallic organic material (TMOM)-based nanostructures combined with the new architectures of metal-organic frameworks (MOFs) are promising candidates for gas-sensing applications. This work is the first to successfully convert MOF nanomaterials into nano-porous carbon through carbon nanotubes (CNT) catalytic reaction via a simple and facile hydrothermal method. The leaf-like nanostructures exhibit a high surface-to-volume ratio of 363 m2 g-1. The TMOM nanostructures were subsequently exposed to different types of target gases for a wide range of gas concentrations at different operating temperatures. The carbon nanotubes (TMOM-CNT) hybrid nanocomposites were characterized using X-ray powder diffraction, X-ray photoelectron spectroscopy, Brunauer-Emmett-Teller, scanning electron microscopy, energy dispersion spectrum analysis, thermo-gravimetric analysis, and transmission electron microscopy. The fabricated Zn-Co-Ni MOF@CNT sensors exhibit high selectivity and gas-sensing response toward H2S gas at an optimal temperature of 325 °C for 100 ppm. These superior gas-sensing performances reveal that the Zn-Co-Ni MOF@CNT sensors with a unique leaf shape exhibit potential applications for the environment applications in gas sensor industry.