Fe─S Bond-Mediated Efficient Electron Transfer in Quantum Dots/Metal-Organic Frameworks for Boosting Photoelectrocatalytic Nitrogen Fixation.

Effective electron supply to produce ammonia in photoelectrochemical nitrogen reduction reaction (PEC NRR) remains challenging due to the sluggish multiple proton-coupled electron transfer and unfavorable carrier recombination. Herein, InP quantum dots decorated with sulfur ligands (InP QDs-S2-) bound to MIL-100(Fe) as a benchmark catalyst for PEC NRR is reported. It is found that MIL-100(Fe) can combined with InP QDs-S2- via Fe─S bonds as bridge to facilitate the electron transfer by experimental results. The formation of Fe─S bonds can facilitate electron transfer from inorganic S2- ligands of InP QDs to the Fe metal sites of MIL-100(Fe) within 52 ps, ensuring a more efficient electron transfer and electron-hole separation confirmed by the time-resolved spectroscopy. More importantly, the process of photo-induced carrier transfer can be traced by in situ attenuated total reflection surface-enhanced infrared tests, certifying that the effective electron transfer can promote N≡N dissociation and N2 hydrogenation. As a result, InP QDs-S2-/MIL-100(Fe) exhibits prominent performance with an outstanding NH3 yield of 0.58 µmol cm-2 h-1 (3.09 times higher than that of MIL-100(Fe)). This work reveals an important ultrafast dynamic mechanism for PEC NRR in QDs modified metal-organic frameworks, providing a new guideline for the rational design of efficient MOFs photocathodes.

Vacancy-Mediated Control of Local Electronic Structure for High-Efficiency Electrocatalytic Conversion of N2 to NH3.

Ambient electrocatalytic nitrogen (N2 ) reduction has gained significant recognition as a potential substitute for producing ammonia (NH3 ). However, N2 adsorption and *NN protonation for N2 activation reaction with the competing hydrogen evolution reaction remain a daunting challenge. Herein, a defect-rich TiO2 nanosheet electrocatalyst with PdCu alloy nanoparticles (PdCu/TiO2-x ) is designed to elucidate the reactivity and selectivity trends of N2 cleavage path for N2 -to-NH3 catalytic conversion. The introduction of oxygen vacancy (OV) not only acts as active sites but also effectively promotes the electron transfer from Pd-Cu sites to high-concentration Ti3+ sites, and thus lends to the N2 activation via electron donation of PdCu. OVs-mediated control effectively lowers the reaction barrier of *N2 H and *H adsorption and facilitates the first hydrogenation process of N2 activation. Consequently, PdCu/TiO2-x catalyst attains a high rate of NH3 evolution, reaching 5.0 mmol gcat. -1  h-1 . This work paves a pathway of defect-engineering metal-supported electrocatalysts for high-efficient ammonia electrosynthesis.

Self-Supported Pd Nanorod Arrays for High-Efficient Nitrate Electroreduction to Ammonia.

Electrochemical nitrate (NO3 - ) reduction to ammonia (NH3 ) offers a promising pathway to recover NO3 - pollutants from industrial wastewater that can balance the nitrogen cycle and sustainable green NH3 production. However, the efficiency of electrocatalytic NO3 - reduction to NH3 synthesis remains low for most of electrocatalysts due to complex reaction processes and severe hydrogen precipitation reaction. Herein, high performance of nitrate reduction reaction (NO3 - RR) is demonstrated on self-supported Pd nanorod arrays in porous nickel framework foam (Pd/NF). It provides a lot of active sites for H* adsorption and NO3 - activation leading to a remarkable NH3 yield rate of 1.52 mmol cm-2  h-1 and a Faradaic efficiency of 78% at -1.4 V versus RHE. Notably, it maintains a high NH3 yield rate over 50 cycles in 25 h showing good stability. Remarkably, large-area Pd/NF electrode (25 cm2 ) shows a NH3 yield of 174.25 mg h-1 , be promising candidate for large-area device for industrial application. In situ FTIR spectroscopy and density functional theory calculations analysis confirm that the enrichment effect of Pd nanorods encourages the adsorption of H species for ammonia synthesis following a hydrogenation mechanism. This work brings a useful strategy for designing NO3 - RR catalysts of nanorod arrays with customizable compositions.

Cascade N2 Reduction Process with DBD Plasma Oxidation and Electrocatalytic Reduction for Continuous Ammonia Synthesis.

Due to the extremely high bond energy of N≡N (∼941 kJ/mol), the traditional Haber-Bosch process of ammonia synthesis is known as an energy-intensive and high CO2-emission industry. In this paper, a cascade N2 reduction process with dielectric barrier discharge (DBD) plasma oxidation and electrocatalytic reduction as an alternative route is first proposed. N2 is oxidized to be reactive nitrogen species (RNS) by nonthermal plasma, which would then be absorbed by KOH solution and electroreduced to NH4+. It is found that the production of NOx is a function of discharge length, discharge power, and gas flow rate. Afterward, the cobalt catalyst is used in the process of electrocatalytic reduction of ammonia, which shows high selectivity (Faradic efficiency (FE) above 90%) and high yield of ammonia (45.45 mg/h). Finally, the cascade plasma oxidation and electrocatalytic reduction for ammonia synthesis is performed. Also, the performance of the reaction system is evaluated. It is worth mentioning that a stable and sustainable ammonia production efficiency of 16.21 mg/h is achieved, and 22.16% of NOx obtained by air activation is converted into NH4+. This work provides a demonstration for further industrial application of ammonia production with DBD plasma oxidation and electrocatalytic reduction techniques.

Response Analysis of the Three-Degree-of-Freedom Vibroimpact System with an Uncertain Parameter.

The inherent non-smoothness of the vibroimpact system leads to complex behaviors and a strong sensitivity to parameter changes. Unfortunately, uncertainties and errors in system parameters are inevitable in mechanical engineering. Therefore, investigations of dynamical behaviors for vibroimpact systems with stochastic parameters are highly essential. The present study aims to analyze the dynamical characteristics of the three-degree-of-freedom vibroimpact system with an uncertain parameter by means of the Chebyshev polynomial approximation method. Specifically, the vibroimpact system model considered is one with unilateral constraint. Firstly, the three-degree-of-freedom vibroimpact system with an uncertain parameter is transformed into an equivalent deterministic form using the Chebyshev orthogonal approximation. Then, the ensemble means responses of the stochastic vibroimpact system are derived. Numerical simulations are performed to verify the effectiveness of the approximation method. Furthermore, the periodic and chaos motions under different system parameters are investigated, and the bifurcations of the vibroimpact system are analyzed with the Poincaré map. The results demonstrate that both the restitution coefficient and the random factor can induce the appearance of the periodic bifurcation. It is worth noting that the bifurcations fundamentally differ between the stochastic and deterministic systems. The former has a bifurcation interval, while the latter occurs at a critical point.

Carbon Dots Mediated In Situ Confined Growth of Bi Clusters on g-C3 N4 Nanomeshes for Boosting Plasma-Assisted Photoreduction of CO2.

Synthesis of high-efficiency, cost-effective, and stable photocatalysts has long been a priority for sustainable photocatalytic CO2 reduction reactions (CRR), given its importance in achieving carbon neutrality goals under the new development philosophy. Fundamentally, the sluggish interface charge transportation and poor selectivity of products remain a challenge in the CRR progress. Herein, this work unveils a synergistic effect between high-density monodispersed Bi/carbon dots (CDs) and ultrathin graphite phase carbon nitride (g-C3 N4 ) nanomeshes for plasma-assisted photocatalytic CRR. The optimal g-C3 N4 /Bi/CDs heterojunction displays a high selectivity of 98% for CO production with a yield up to 22.7 µmol g-1 without any sacrificial agent. The in situ confined growth of plasmonic Bi clusters favors the production of more hot carriers and improves the conductivity of g-C3 N4 . Meanwhile, a built-in electric field driving force modulates the directional injection photogenerated holes from plasmonic Bi clusters and g-C3 N4 photosensitive units to adjacent CDs reservoirs, thus promoting the rapid separation and oriented transfer in the CRR process. This work sheds light on the mechanism of plasma-assisted photocatalytic CRR and provides a pathway for designing highly efficient plasma-involved photocatalysts.

A Tandem 0D/2D/2D NbS2 Quantum Dot/Nb2 O5 Nanosheet/g-C3 N4 Flake System with Spatial Charge-Transfer Cascades for Boosting Photocatalytic Hydrogen Evolution.

The relatively high recombination rate of charges remains the most critical limiting factor for solar-driven water splitting for hydrogen generation. Herein, a tandem 0D/2D/2D NbS2 quantum dot/Nb2 O5 nanosheet/g-C3 N4 flake (NSNOCN) system is designed. Owing to the unique spatial-arrangement and elaborate morphology of 0D NbS2 , 2D Nb2 O5 , and 2D g-C3 N4 in the newly designed NSNOCN, plenty of spatial charge-transfer cascades from g-C3 N4 to NbS2 via Nb2 O5 are formed to accelerate separation and transfer of charges significantly, thus contributing to a high photocatalytic H2 generation rate of 13.99 mmol h-1 g-1 (an apparent quantum efficiency of 10.8% at 420 nm), up to 107.6 and 43.7 times by contrast with that of g-C3 N4 and Nb2 O5 , respectively. This work can provide a new platform in the design of artificial photocatalytic systems with high charge-transfer efficiency.

Surface Hydrogen Atoms Promote Oxygen Activation for Solar Light-Driven NO Oxidization over Monolithic α-Ni(OH)2/Ni Foam.

Catalysis oxidization has been known to be an effective technique in environmental remediation. However, low efficiency for oxygen activation and difficult recovery of the catalysts in powdery form significantly limit the practical application. In this work, a new-type monolithic α-Ni(OH)2/Ni-foam was fabricated by the hydrothermal process. We found that H atoms of α-Ni(OH)2 can significantly promote oxygen activation, which endows it with favorable NO and NO2 oxidization confirmed by theoretical calculation and in situ DRIFTS. Furthermore, the introduction of Ni foam accelerated the pollutant gas transfer and charge carriers' separation because of its abundant porous structure and high conductivity and its monolithic property simplified the recycling operation. Consequently, the obtained α-Ni(OH)2/Ni-foam achieved an excellent NO oxidation (69.0%) and no toxic NO2 was detected under visible light illumination (λ > 420 nm), indicating its highly promising potential in environmental remediation. Our work provides a conceptually different fresh perception to promote oxygen activation for highly efficient gas purification.

Stacking-Layer-Number Dependence of Water Adsorption in 3D Ordered Close-Packed g-C3 N4 Nanosphere Arrays for Photocatalytic Hydrogen Evolution.

Water adsorption capacity is a key factor to influence the photocatalytic H2 evolution activity of polymeric g-C3 N4 . Herein, we report the synthesis of 3D ordered close-packed g-C3 N4 nanosphere arrays (CNAs) that significantly enhance the water adsorption capacity. Through precisely controlling the average stacking-layer number (ASLN) of the nanospheres in CNAs, we reveal an interesting stacking-layer-number dependence of water adsorption in the newly designed CNAs for accelerating the H2 evolution reaction, which can be attributed to the differences in adsorption surface areas and adsorption sites endowed by the point-defect cavities in sample CNAs.

Bifurcation analysis of a noisy vibro-impact oscillator with two kinds of fractional derivative elements.

To the best of authors' knowledge, little work was referred to the study of a noisy vibro-impact oscillator with a fractional derivative. Stochastic bifurcations of a vibro-impact oscillator with two kinds of fractional derivative elements driven by Gaussian white noise excitation are explored in this paper. We can obtain the analytical approximate solutions with the help of non-smooth transformation and stochastic averaging method. The numerical results from Monte Carlo simulation of the original system are regarded as the benchmark to verify the accuracy of the developed method. The results demonstrate that the proposed method has a satisfactory level of accuracy. We also discuss the stochastic bifurcation phenomena induced by the fractional coefficients and fractional derivative orders. The important and interesting result we can conclude in this paper is that the effect of the first fractional derivative order on the system is totally contrary to that of the second fractional derivative order.

Response analysis of a class of quasi-linear systems with fractional derivative excited by Poisson white noise.

The Poisson white noise, as a typical non-Gaussian excitation, has attracted much attention recently. However, little work was referred to the study of stochastic systems with fractional derivative under Poisson white noise excitation. This paper investigates the stationary response of a class of quasi-linear systems with fractional derivative excited by Poisson white noise. The equivalent stochastic system of the original stochastic system is obtained. Then, approximate stationary solutions are obtained with the help of the perturbation method. Finally, two typical examples are discussed in detail to demonstrate the effectiveness of the proposed method. The analysis also shows that the fractional order and the fractional coefficient significantly affect the responses of the stochastic systems with fractional derivative.

Structural characterization and human gut microbiota fermentation in vitro of a polysaccharide from Fucus vesiculosus.

In this study, an acidic polysaccharide (FVP-7 A) was isolated from Fucus vesiculosus by DEAE-Sepharose™ fast flow. The chemical composition, glycosidic bonds and in vitro fecal fermentation characteristics of FVP-7 A were studied. Results shown that FVP-7 A was a homogenous polysaccharide with average molecular weight of 30.94 kDa. Combined with FT-IR, monosaccharide composition, methylation and NMR analysis, the glycosidic bonds of FVP-7 A mainly composed of →4)-ß-D-Manp-(1→, →3)-α-L-Fucp-(1→, α-D-Manp-(1→, →3)-ß-D-Manp-(1 â†’ and →4,6)-α-D-Manp-(1→. The zeta potential and atomic force microscopy images indicated that FVP-7 A could exist stably as a single chain-like structure in dilute solution. After gut fermentation, FVP-7 A was utilized and promoted multiple short-chain fatty acids production, especially acetic acid, butyric acid and valeric acid. For prebiotics, FVP-7 A significantly increased the relative abundance of short-chain fatty acids producing bacteria such as Bacteroides, Lachnospira, Faecalibacterium, Ruminococcus, Oscillospira and Dialister, and inhiited the growth of the harmful bacteria Shigella. These results indicated that FVP-7 A could be used as a potential dietary supplement to improve intestinal health.

Efficient ammonia synthesis from the air using tandem non-thermal plasma and electrocatalysis at ambient conditions.

While electrochemical N2 reduction presents a sustainable approach to NH3 synthesis, addressing the emission- and energy-intensive limitations of the Haber-Bosch process, it grapples with challenges in N2 activation and competing with pronounced hydrogen evolution reaction. Here we present a tandem air-NOx-NOx--NH3 system that combines non-thermal plasma-enabled N2 oxidation with Ni(OH)x/Cu-catalyzed electrochemical NOx- reduction. It delivers a high NH3 yield rate of 3 mmol h-1 cm-2 and a corresponding Faradaic efficiency of 92% at -0.25 V versus reversible hydrogen electrode in batch experiments, outperforming previously reported ones. Furthermore, in a flow mode concurrently operating the non-thermal plasma and the NOx- electrolyzer, a stable NH3 yield rate of approximately 1.25 mmol h-1 cm-2 is sustained over 100 h using pure air as the intake. Mechanistic studies indicate that amorphous Ni(OH)x on Cu interacts with hydrated K+ in the double layer through noncovalent interactions and accelerates the activation of water, enriching adsorbed hydrogen species that can readily react with N-containing intermediates. In situ spectroscopies and density functional theory (DFT) results reveal that NOx- adsorption and their hydrogenation process are optimized over the Ni(OH)x/Cu surface. This work provides new insights into electricity-driven distributed NH3 production using natural air at ambient conditions.

Spiro-Josiphos Ligands for the Ir-Catalyzed Asymmetric Synthesis of Chiral Amines under Hydrogenation Conditions.

Transition metal-catalyzed asymmetric hydrogenation possesses unparalleled advantages to prepare chiral amines. Here we reported a novel ligand that combined Josiphos and a spirobiindane scaffold and simultaneously investigated its application in Ir-catalyzed asymmetric hydrogenation for the synthesis of chiral amines. Excellent catalytic activity (5000 TON), high enantioselectivity (up to 99% ee), and broad substrate scope (different C═N substrates) make it highly promising for both academic research and industrial applications.

Hydroxyl-Bonded Co Single Atom Site on Boroncarbonitride Surface Realizes Nonsacrificial H2O2 Synthesis in the Near-Infrared Region.

Photocatalytic synthesis of hydrogen peroxide (H2O2) from O2 and H2O under near-infrared light is a sustainable renewable energy production strategy, but challenging reaction. The bottleneck of this reaction lies in the regulation of O2 reduction path by photocatalyst. Herein, the center of the one-step two-electron reduction (OSR) pathway of O2 for H2O2 evolution via the formation of the hydroxyl-bonded Co single-atom sites on boroncarbonitride surface (BCN-OH2/Co1) is constructed. The experimental and theoretical prediction results confirm that the hydroxyl group on the surface and the electronic band structure of BCN-OH2/Co1 are the key factor in regulating the O2 reduction pathway. In addition, the hydroxyl-bonded Co single-atom sites can further enrich O2 molecules with more electrons, which can avoid the one-electron reduction of O2 to •O2 -, thus promoting the direct two-electron activation hydrogenation of O2. Consequently, BCN-OH2/Co1 exhibits a high H2O2 evolution apparent quantum efficiency of 0.8% at 850 nm, better than most of the previously reported photocatalysts. This study reveals an important reaction pathway for the generation of H2O2, emphasizing that precise control of the active site structure of the photocatalyst is essential for achieving efficient conversion of solar-to-chemical.

Black Ultrathin Single-Crystalline Flakes of CuVP2S6 and CuCrP2S6 for Near-Infrared-Driven Photocatalytic Hydrogen Evolution.

The development of new near-infrared-responsive photocatalysts is a fascinating and challenging approach to acquire high photocatalytic hydrogen evolution (PHE) performance. Herein, near-infrared-responsive black CuVP2S6 and CuCrP2S6 flakes, as well as CuInP2S6 flakes, are designed and constructed for PHE. Atom-resolved scanning transmission electron microscopy images and X-ray absorption fine structure evidence the formation of ultrathin single-crystalline sheet-like structure of CuVP2S6 and CuCrP2S6. The synthetic CuVP2S6 and CuCrP2S6, with a narrow bandgap of ≈1.0 eV, shows the high light-absorption edge exceeding 1100 nm. Moreover, through the femtosecond-resolved transient absorption spectroscopy, CuCrP2S6 displays the efficient charge transfer and long charge lifetime (18318.1 ps), which is nearly 3 and 29 times longer than that of CuVP2S6 and CuInP2S6, respectively. In addition, CuCrP2S6, with the appropriate d-band and p-band, is thermodynamically favorable for the H+ adsorption and H2 desorption by contrast with CuVP2S6 and CuInP2S6. As a result, CuCrP2S6 exhibits high PHE rates of 9.12 and 0.66 mmol h-1 g-1 under simulated sunlight and near-infrared light irradiation, respectively, far exceeding other layered metal phospho-sulfides. This work offers a distinctive perspective for the development of new near-infrared-responsive photocatalysts.

An electron-hole rich dual-site nickel catalyst for efficient photocatalytic overall water splitting.

Photocatalysis offers an attractive strategy to upgrade H2O to renewable fuel H2. However, current photocatalytic hydrogen production technology often relies on additional sacrificial agents and noble metal cocatalysts, and there are limited photocatalysts possessing overall water splitting performance on their own. Here, we successfully construct an efficient catalytic system to realize overall water splitting, where hole-rich nickel phosphides (Ni2P) with polymeric carbon-oxygen semiconductor (PCOS) is the site for oxygen generation and electron-rich Ni2P with nickel sulfide (NiS) serves as the other site for producing H2. The electron-hole rich Ni2P based photocatalyst exhibits fast kinetics and a low thermodynamic energy barrier for overall water splitting with stoichiometric 2:1 hydrogen to oxygen ratio (150.7 µmol h-1 H2 and 70.2 µmol h-1 O2 produced per 100 mg photocatalyst) in a neutral solution. Density functional theory calculations show that the co-loading in Ni2P and its hybridization with PCOS or NiS can effectively regulate the electronic structures of the surface active sites, alter the reaction pathway, reduce the reaction energy barrier, boost the overall water splitting activity. In comparison with reported literatures, such photocatalyst represents the excellent performance among all reported transition-metal oxides and/or transition-metal sulfides and is even superior to noble metal catalyst.

Reconstructed Ir‒O‒Mo species with strong Brønsted acidity for acidic water oxidation.

Surface reconstruction generates real active species in electrochemical conditions; rational regulating reconstruction in a targeted manner is the key for constructing highly active catalyst. Herein, we use the high-valence Mo modulated orthorhombic Pr3Ir1-xMoxO7 as model to activate lattice oxygen and cations, achieving directional and accelerated surface reconstruction to produce self-terminated Ir‒Obri‒Mo (Obri represents the bridge oxygen) active species that is highly active for acidic water oxidation. The doped Mo not only contributes to accelerated surface reconstruction due to optimized Ir‒O covalency and more prone dissolution of Pr, but also affords the improved durability resulted from Mo-buffered charge compensation, thereby preventing fierce Ir dissolution and excessive lattice oxygen loss. As such, Ir‒Obri‒Mo species could be directionally generated, in which the strong Brønsted acidity of Obri induced by remaining Mo assists with the facilitated deprotonation of oxo intermediates, following bridging-oxygen-assisted deprotonation pathway. Consequently, the optimal catalyst exhibits the best activity with an overpotential of 259 mV to reach 10 mA cmgeo-2, 50 mV lower than undoped counterpart, and shows improved stability for over 200 h. This work provides a strategy of directional surface reconstruction to constructing strong Brønsted acid sites in IrOx species, demonstrating the perspective of targeted electrocatalyst fabrication under in situ realistic reaction conditions.

Spatial Position Regulation of Cu Single Atom Site Realizes Efficient Nanozyme Photocatalytic Bactericidal Activity.

Recently, single-atom nanozymes have made significant progress in the fields of sterilization and treatment, but their catalytic performance as substitutes for natural enzymes and drugs is far from satisfactory. Here, a method is reported to improve enzyme activity by adjusting the spatial position of a single-atom site on the nanoplatforms. Two types of Cu single-atom site nanozymes are synthesized in the interlayer (CuL /PHI) and in-plane (CuP /PHI) of poly (heptazine imide) (PHI) through different synthesis pathways. Experimental and theoretical analysis indicates that the interlayer position of PHI can effectively adjust the coordination number, coordination bond length, and electronic structure of Cu single atoms compared to the in-plane position, thereby promoting photoinduced electron migration and O2 activation, enabling effective generate reactive oxygen species (ROS). Under visible light irradiation, the photocatalytic bactericidal activity of CuL /PHI against aureus is ≈100%, achieving the same antibacterial effect as antibiotics, after 10 min of low-dose light exposure and 2 h of incubation.

Boosting charge-transfer in tuned Au nanoparticles on defect-rich TiO2 nanosheets for enhancing nitrogen electroreduction to ammonia production.

The electrocatalytic nitrogen reduction reaction (eNRR) to ammonia (NH3) has been recognized as an effective, carbon-neutral, and great-potential strategy for ammonia production. However, the conversion efficiency and selectivity of eNRR still face significant challenges due to the slow transfer kinetics and lack of effective N2 adsorption and activation sites in this process. Herein, we designed and fabricated defect-rich TiO2 nanosheets furnished with oxygen vacancies (OVs) and Au nanoparticles (Au/TiO2-x) as the electrocatalyst for efficient N2-fixing. The experimental results demonstrate that OVs act as active sites, which enable efficient chemisorption and activation of N2 molecules. The Au nanoparticles loaded on the OVs-rich TiO2 nanosheets not only accelerate charge transfer but also change the local electronic structure, thus enhancing N2 adsorption and activation. In this work, the optimal Au/TiO2-x electrocatalyst displays a considerable NH3 yield activity of 12.5 µg h-1 mgcat.-1 and a faradaic efficiency (FE) of 10.2 % at -0.40 V vs reversible hydrogen electrode (RHE). More importantly, the Au/TiO2-x exhibits a stable N2-fixing activity in cycling and it persists even after 80 h of consecutive electrolysis. Density functional theory (DFT) calculations reveal that the OVs serve as the active sites in TiO2, while Au nanoparticles are crucial for improving N2 chemisorption and lowering the reaction energy barrier by facilitating the charge transfer for eNRR with a distal hydrogenation pathway. This research offers a rational catalytic site design for modulating charge transfer of active sites on metal-supported defective catalysts to boost N2 electroreduction to NH3.