Cascaded *CO-*COH Intermediates on a Nonmetallic Plasmonic Photocatalyst for CO2-to-C2H6 with 90.6 % Selectivity.

Oxygen vacancies (OV) in nonmetallic plasmonic photocatalysts can decrease the energy barrier for CO2 reduction, boosting C1 intermediate production for potential C2 formation. However, their susceptibility to oxidation weakens C1 intermediate adsorption. Herein we proposed a "photoelectron injection" strategy to safeguard OV in W18O49 by creating a W18O49/ZIS (W/Z) plasmonic photocatalyst. Moreover, photoelectrons contribute to the local multi-electron environment of W18O49, enhancing the intrinsic excitation of its hot electrons with extended lifetimes, as confirmed by in situ XPS and femtosecond transient absorption analysis. Density functional theory calculations revealed that W/Z with OV enhances CO2 adsorption, activating *CO production, while reducing the energy barrier for *COH production (0.054 eV) and subsequent *CO-*COH coupling (0.574 eV). Successive hydrogenation revealed that the free energy for *CH2CH2 hydrogenation (0.108 eV) was lower than that for *CH2CH2 desorption for C2H4 production (0.277 eV), favouring C2H6 production. Consequently, W/Z achieves an efficient C2H6 activity of 653.6 µmol g-1 h-1 under visible light, with an exceptionally high selectivity of 90.6 %. This work offers a new strategy for the rational design of plasmonic photocatalysts with high selectivity for C2+ products.

RBF neural network disturbance observer-based backstepping boundary vibration control for Euler-Bernoulli beam model with input saturation.

The main objective of this paper is to address the issue of vibration control for a class of Euler-Bernoulli beam systems that are subject to external disturbances and input saturation. The proposed controller differs from other backstepping methods in that it employs a radial basis function (RBF) neural network to accurately estimate boundary disturbances and incorporates the hyperbolic tangent function to ensure input constraints. The nonlinear partial differential equation (PDE) model is initially derived based on Hamilton's principle to capture the dominant dynamic characteristics of the flexible beam. In the framework of the Lyapunov direct approach, an adaptive RBF neural network-based law is subsequently designed to estimate the state-related boundary disturbances. The backstepping approach is then developed to propose sufficient conditions for ensuring the stability and convergence of closed-loop systems subject to input saturation. Finally, the effectiveness and superiority of the proposed methodology are further demonstrated by comparing the simulation results of constrained backstepping controllers.

Achieving Long-Lived Charge Separated State through Ultrafast Interfacial Hole Transfer in Redox Sites-Isolated CdS Nanorods for Enhanced Photocatalysis.

As opposed to natural photosynthesis, a significant challenge in a semiconductor-based photocatalyst is the limited hole extraction efficiency, which adversely affects solar-to-fuel efficiency. Recent studies have demonstrated that photocatalysts featuring spatially isolated dual catalytic oxidation/reduction sites can yield enhanced hole extraction efficiencies. However, the decay dynamics of excited states in such photocatalysts have not been explored. Here a ternary barbell-shaped CdS/MoS2/Cu2S heterostructure is prepared, comprising CdS nanorods (NRs) interfaced with MoS2 nanosheets at both ends and Cu2S nanoparticles on the sidewall. By using transient absorption (TA) spectra, highly efficient charge separation within the CdS/MoS2/Cu2S heterostructure are identified. This is achieved through directed electron transfer to the MoS2 tips at a rate constant of >8.3 × 109 s-1 and rapid hole transfer to the Cu2S nanoparticles on the sidewall at a rate of >6.1 × 1010 s-1, leading to an exceptional overall charge transfer constant of 2.3 × 1011 s-1 in CdS/MoS2/Cu2S. The enhanced hole transfer efficiency results in a remarkably prolonged charge-separated state, facilitating efficient electron accumulation within the MoS2 tips. Consequently, the ternary CdS/MoS2/Cu2S heterostructure demonstrates a 22-fold enhancement in visible-light-driven H2 generation compare to pure CdS nanorods. This work highlights the significance of efficient hole extraction in enhancing the solar-to-H2 performance of semiconductor-based heterostructure.

Strong Interfacial Chemical Bonding in Regulating Electron Transfer and Stabilizing Catalytic Sites in a Metal-Semiconductor Schottky Junction for Enhanced Photocatalysis.

The weak electronic interaction at metal-photocatalyst heterointerfaces often compromises solar-to-fuel performance. Here, a trifunctional Schottky junction, involving chemically stabilized ultrafine platinum nanoparticles (Pt NPs, ≈3 nm in diameter) on graphitic carbon nitride nanosheets (CNs) is proposed. The Pt-CN electronic interaction induces a 1.5% lattice compressive strain in Pt NPs and maintains their ultrafine size, effectively preventing their aggregation during photocatalytic reactions. Density functional theory calculations further demonstrate a significant reduction in the Schottky barrier at the chemically bonded CN-Pt heterointerface, facilitating efficient interfacial electron transfer, as supported by femtosecond transient absorption spectra (fs-TAS) measurements. The combined effects of lattice strain, stabilized Pt NPs, and efficient interfacial charge transport collaboratively enhance the photocatalytic performance, leading to over an 11-fold enhancement in visible light H2 production (8.52 mmol g-1 h-1) compared to the CN nanosheets with the in situ photo-deposited Pt NPs (0.76 mmol g-1 h-1). This study highlights the effectiveness of strong metal-semiconductor electronic interactions and underscores the potential for developing high-efficiency photocatalysts.

Synchronizing Efficient Purification of VOCs in Durable Solar Water Evaporation over a Highly Stable Cu/W18O49@Graphene Material.

Solar-driven clean water production is challenged by VOCs (volatile organic compounds), which pose health risks in distilled water. Herein, we developed a Cu/W18O49@Graphene photothermal-photocatalytic material addressing VOCs contamination. Plasmonic coupling between Cu and W18O49 enhances light absorption, and 1-2 layers of graphene encapsulation protects oxygen vacancies within W18O49 while facilitating hot electron extraction, effectively mitigating their ultrafast relaxation. Density functional theory calculations revealed enhanced VOCs adsorption on graphene. These synergies address oxygen vacancy decay in W18O49 and provide more active sites for gas-liquid-solid triphase photocatalytic reactions. Integrated with a three-dimensional floating evaporator substrate, the optimized Cu/W18O49@Graphene material achieved an effective water evaporation rate of 1.41 kg m-2 h-1 (efficiency of 88.6%), exceptional stability (>120 h), and remarkable 99% phenol removal under 1 sun irradiation (1 kW m-2). This work provides a promising solution to mitigate VOCs contamination in solar-driven water evaporation.

Bidirectional manipulation of iodine redox kinetics in aqueous Fe-I2 electrochemistry.

Catalyzing conversion is a promising approach to unlock the theoretical potentials of the I2/I- redox couple in aqueous Fe-I2 electrochemistry. However, most reported results only obtain one-directional efficient iodine conversion and cannot realize a balance of full reduction and reoxidation, thereby resulting in rapid capacity decay and/or low coulombic efficiency. Herein, the concept of bidirectional catalysis based on a core-shell structured composite cathode design, which accelerates the formation and the decomposition of FeI2 simultaneously during battery dynamic cycling, is proposed to regulate the Fe-I2 electrochemical reactions. Notably, the functional matrix integrates N, P co-doping and FeP nanocrystals into a carbon shell to achieve bidirectional catalysis. More specifically, the carbon shell acts as a physical barrier to effectively capture active species within its confined environment, N, P heteroatoms function better in directing the iodine reduction and FeP facilitates the decomposition of FeI2. As confirmed with in situ and ex situ analysis, the Fe-I2 cell operates a one-step but reversible I2/FeI2 pair with enhanced kinetics. Consequently, the composite cathode exhibits a reversible Fe2+ storage capability of 202 mA h g-1 with a capacity fading rate of 0.016% per cycle over 500 cycles. Further, a stable pouch cell was fabricated and yielded an energy density of 146 W h kgiodine-1. Moreover, postmortem analysis reveals that the capacity decay of the Fe-I2 cell originates from anodic degradation rather than the accumulation of inactive iodine. This study represents a promising direction to manipulate iodine redox in rechargeable metal-iodine batteries.

Ppb-level NH3 photoacoustic sensor combining a hammer-shaped tuning fork and a 9.55 µm quantum cascade laser.

We present a quartz enhanced photoacoustic spectroscopy (QEPAS) gas sensor designed for precise monitoring of ammonia (NH3) at ppb-level concentrations. The sensor is based on a novel custom quartz tuning fork (QTF) with a mid-infrared quantum cascade laser emitting at 9.55 µm. The custom QTF with a hammer-shaped prong geometry which is also modified by surface grooves is designed as the acoustic transducer, providing a low resonance frequency of 9.5 kHz and a high-quality factor of 10263 at atmospheric pressure. In addition, a temperature of 50 °C and a large gas flow rate of 260 standard cubic centimeters per minute (sccm) are applied to mitigate the adsorption and desorption effect arising from the polarized molecular of NH3. With 80-mW optical power and 300-ms lock-in integration time, the detection limit is achieved to be 2.2 ppb which is the best value reported in the literature so far for NH3 QEPAS sensors, corresponding to a normalized noise equivalent absorption coefficient of 1.4 × 10-8 W cm-1 Hz-1/2. A five-day continuous monitoring for atmospheric NH3 is performed, verifying the stability and robustness of the presented QEPAS-based NH3 sensor.

Impacts of Ship Emissions on Air Quality in Southern China: Opportunistic Insights from the Abrupt Emission Changes in Early 2020.

In early 2020, two unique events perturbed ship emissions of pollutants around Southern China, proffering insights into the impacts of ship emissions on regional air quality: the decline of ship activities due to COVID-19 and the global enforcement of low-sulfur (<0.5%) fuel oil for ships. In January and February 2020, estimated ship emissions of NOx, SO2, and primary PM2.5 over Southern China dropped by 19, 71, and 58%, respectively, relative to the same period in 2019. The decline of ship NOx emissions was mostly over the coastal waters and inland waterways of Southern China due to reduced ship activities. The decline of ship SO2 and primary PM2.5 emissions was most pronounced outside the Chinese Domestic Emission Control Area due to the switch to low-sulfur fuel oil there. Ship emission reductions in early 2020 drove 16 to 18% decreases in surface NO2 levels but 3.8 to 4.9% increases in surface ozone over Southern China. We estimated that ship emissions contributed 40% of surface NO2 concentrations over Guangdong in winter. Our results indicated that future abatements of ship emissions should be implemented synergistically with reductions of land-borne anthropogenic emissions of nonmethane volatile organic compounds to effectively alleviate regional ozone pollution.

Provenance of Aerosol Black Carbon over Northeast Indian Ocean and South China Sea and Implications for Oceanic Black Carbon Cycling.

Aerosol black carbon (BC) is a short-lived climate pollutant. The poorly constrained provenance of tropical marine aerosol BC hinders the mechanistic understanding of extreme climate events and oceanic carbon cycling. Here, we collected PM2.5 samples during research cruise NORC2016-10 through South China Sea (SCS) and Northeast Indian Ocean (NEIO) and measured the dual-carbon isotope compositions (δ13C-Δ14C) of BC using hydrogen pyrolysis technique. Aerosol BC exhibits six different δ13C-Δ14C isotopic spaces (i.e., isotope provinces). Liquid fossil fuel combustion, from shipping emissions and adjacent land, is the predominant source of BC over isotope provinces "SCS close to Chinese Mainland" (53.5%), "Malacca Strait" (53.4%), and "Open NEIO" (40.7%). C3 biomass burning is the major contributor to BC over isotope provinces "NEIO close to Southeast Asia" (55.8%), "Open NEIO" (41.3%), and "Open SCS" (40.0%). Coal combustion and C4 biomass burning show higher contributions to BC over "Sunda Strait" and "Open SCS" than the others. Overall, NEIO near the Bay of Bengal, Malacca Strait, and north SCS are three hot spots of fossil fuel-derived BC; the first two areas are also hot spots of biomass-derived BC. The comparable δ13C-Δ14C between BC in aerosol and dissolved BC in surface seawater may suggest atmospheric BC deposition as a potential source of oceanic dissolved BC.

Chitosan-assisted synthesis of 1D g-C3N4 nanorods for enhanced photocatalysis.

1D porous g-C3N4 nanorods were synthesized using chitosan as a template, offering a large surface area and enhanced visible light absorption. These nanorods exhibited a remarkable 8.3-fold increase in H2 generation rate (26.6 µmol h-1) compared to bulk g-C3N4.

Impact of Ship Emissions on Air Quality in the Greater Bay Area in China under the Latest Global Marine Fuel Regulation.

As the main anthropogenic source in open seas and coastal areas, ship emissions impact the climate, air quality, and human health. The latest marine fuel regulation with a sulfur content limit of 0.5% went into effect globally on January 1, 2020. Investigations of ship emissions after fuel switching are necessary. In this study, online field measurements at an urban coastal site and modeling simulations were conducted to detect the impact of ship emissions on air quality in the Greater Bay Area (GBA) in China under new fuel regulation. By utilizing a high mass-resolution single particle mass spectrometer, the vanadium(V) signal was critically identified and was taken as a robust indicator for ship-emitted particles (with relative peak area > 0.1). The considerable number fractions of high-V particles (up to 30-40% during ship plumes) indicated that heavy fuel oils via simple desulfurization or blending processes with low-sulfur fuels were extensively used in the GBA to meet the global 0.5% sulfur cap. Our results showed that ship-emitted particulate matter and NOx contributed up to 21.4% and 39.5% to the ambient, respectively, in the summertime, significantly affecting the air quality in the GBA. The sea-land breeze circulation also played an important role in the transport pattern of ship-emitted pollutants in the GBA.

A π-Conjugated Van der Waals Heterostructure Between Single-Atom Ni-Anchored Salphen-Based Covalent Organic Framework and Polymeric Carbon Nitride for High-Efficiency Interfacial Charge Separation.

Semiconductor-based heterostructures have exhibited great promise as a photocatalyst to convert solar energy into sustainable chemical fuels, however, their solar-to-fuel efficiency is largely restricted by insufficient interfacial charge separation and limited catalytically active sites. Here the integration of high-efficiency interfacial charge separation and sufficient single-atom metal active sites in a 2D van der Waals (vdW) heterostructure between ultrathin polymeric carbon nitride (p-CN) and Ni-containing Salphen-based covalent organic framework (Ni-COF) nanosheets is illustrated. The results reveal a NiN2 O2 chemical bonding in NiCOF nanosheets, leading to a highly separated single-atom Ni sites, which will function as the catalytically active sites to boost solar fuel production, as confirmed by X-ray absorption spectra and density functional theory calculations. Using ultrafast femtosecond transient adsorption (fs-TA) spectra, it shows that the vdW p-CN/Ni-COF heterostructure exhibits a faster decay lifetime of the exciton annihilation (τ = 18.3 ps) compared to that of neat p-CN (32.6 ps), illustrating an efficiently accelerated electron transfer across the vdW heterointerface from p-CN to Ni-COF, which thus allows more active electrons available to participate in the subsequent reduction reactions. The photocatalytic results offer a chemical fuel generation rate of 2.29 mmol g-1 h-1 for H2 and 6.2 µmol g-1 h-1 for CO, ≈127 and three times higher than that of neat p-CN, respectively. This work provides new insights into the construction of a π-conjugated vdW heterostructure on promoting interfacial charge separation for high-efficiency photocatalysis.

Diverse changes in shipping emissions around the Western Pacific ports under the coeffect of the epidemic and fuel oil policy.

The Western Pacific Ocean (the WPO), as one of the busiest shipping areas in the world, holds a complex water traffic network. In 2020, the International Maritime Organization (IMO) low-sulfur fuel regulations were implemented globally, while the COVID-19 outbreak influenced shipping activities together. This study aimed to assess the combined impact of epidemics and low-sulfur fuel policies on ship emissions, as well as their environmental effects on the WPO. The ship emission model based on the Automatic Identification System (AIS) data was applied to analyze the monthly emission variations during 2018-2020. It was found that the epidemic had obvious diverse influences on the coastal ports in the WPO. Overall, shipping emissions declined by 15 %-30 % in the first half of 2020 compared with those in 2019 due to the COVID-19 lockdown, whereas they rebounded in the second half as a result of trade recovery. The pollutants discharged per unit of cargo by ships rose after the large-range lockdown. China's multiphase domestic emission control areas (DECAs) and the IMO global low-sulfur fuel regulation have greatly reduced SO2 emissions from ships and caused them to "bypass and come back" to save fuel costs around emission control areas from 2018 to 2020. Based on satellite data and land-based measurements, it was found that the air quality over sea water and coastal cities has shown a positive response to changes in ship-emitted NOx and SO2. Our results reveal that changes in shipping emissions during typical periods, depending on their niches in the complex port traffic network, call for further efforts for cleaner fuel oils, optimized ECA and ship lane coordination in the future. Shipping related air pollutions during the later economic recovery also needs to be addressed after international scale standing-by events.

Resolving Interface Barrier Deviation from the Schottky-Mott Rule: A Mitigation Strategy via Engineering MoS2-Metal van der Waals Contact.

The Schottky barrier (SB) in the ultraclean van der Waals contact between two-dimensional (2D) MoS2 and three-dimensional (3D) indium (In) strikingly deviates from the Schottky-Mott limit (SML). Herein, on the basis of first-principles calculation, the origin of the SB deviation is brought to bear, as well as a strategy for mitigating the SB deviation. In light of the good agreement between the SB and the corrected SB by interface potential difference (ΔV) and Fermi -level shift (ΔEF) based on the SML, the SB deviation is attributed to the combined effects of ΔV and ΔEF. Furthermore, when a Au, Sc, or Ti thin film is coated on the back side of In, the SB deviation and the sum of ΔV and ΔEF decrease similarly. Importantly, in the Ti coating situation, the SB is reduced to 0.12 eV, notably smaller than the value of 0.30 eV in the Au coating case. This interface engineering can be generalized to regulate the SB between a 2D semiconductor and a 3D alloy.

π-Conjugated In-Plane Heterostructure Enables Long-Lived Shallow Trapping in Graphitic Carbon Nitride for Increased Photocatalytic Hydrogen Generation.

The relatively short-lived excited states, such as the nascent electron-hole pairs (excitons) and the shallow trapping states, in semiconductor-based photocatalysts produce an exceptionally high charge carrier recombination rate, dominating a low solar-to-fuel performance. Here, a π-conjugated in-plane heterostructure between graphitic carbon nitride (g-CN) and carbon rings (Crings ) (labeling g-CN/Crings ) is effectively synthesized from the thermolysis of melamine-citric acid aggregates via a microwave-assisted heating process. The g-CN/Crings in-plane heterostructure shows remarkably suppressed excited-state decay and increased charge carrier population in photocatalysis. Kinetics analysis from the femtosecond time-resolved transient absorption spectroscopy illustrates that the g-CN/Crings π-conjugated heterostructure produces slower exciton annihilation (τ1  = 7.9 ps) and longer shallow electron trapping (τ2  = 407.1 ps) than pristine g-CN (τ1  = 3.6 ps, τ2  = 264.1 ps) owing to Crings incorporation, both of which enable more photoinduced electrons to participate in the photocatalytic reactions, thereby realizing photoactivity enhancement. As a result, the photocatalytic activity exhibits an eightfold enhancement in visible-light-driven H2 generation. This work provides a viable route of constructing π-conjugated in-plane heterostructures to suppress the excited-state decay and improve the photocatalytic performance.

Arrays of Ag-nanoparticles decorated TiO2 nanotubes as reusable three-dimensional surface-enhanced Raman scattering substrates for molecule detection.

Three-dimensional surface-enhanced Raman scattering (SERS) substrates usually provide more hot spots in the excitation light beam and higher sensitivity when compared with the two-dimensional counterpart. Here a simple approach is presented for the fabrication of arrays of Ag-nanoparticles decorated TiO2 nanotubes. Arrays of ZnO nanorods were fabricated in advance by a hydrothermal method. Then TiO2 nanotube arrays were achieved by immersing the arrays of ZnO nanorods in an aqueous solution of (NH4)2TiF6 for 1.5 h. Vertically aligned TiO2 nanotube arrays were modified with dense Ag nanoparticles by Ag mirror reaction. High density of Ag nanoparticles decorated on the fabricated TiO2 nanotubes provide plenty of hotspots for Raman enhancement. In addition, the fabricated array of Ag nanoparticles modified TiO2 nanotubes can serve as a reusable SERS substrate because of the photocatalytic activity of the TiO2 nanotubes. The SERS substrate adsorbed with analyte molecules can realize self-cleaning in deionized water after UV irradiation for 2.5 h. The sensitivity of the fabricated SERS substrate was investigated by the detection of organic dye molecules. The detectable concentration limits of rhodamine 6G (R6G), malachite green (MG) and methylene blue (MB) were found to be 10-12 M, 10-9 M and 10-8 M, respectively. The enhancement factor (EF) of the three-dimensional SERS substrate was estimated to be as high as ∼1.4×108. Therefore, the prepared Ag nanoparticles modified TiO2 nanotube arrays have promising potentials to be applied to rapid and trace SERS detection of organic chemicals.

Recovering rare earth elements via immobilized red algae from ammonium-rich wastewater.

Biotreatment of acidic rare earth mining wastewater via acidophilic living organisms is a promising approach owing to their high tolerance to high concentrations of rare earth elements (REEs); however, simultaneous removal of both REEs and ammonium is generally hindered since most acidophilic organisms are positively charged. Accordingly, immobilization of acidophilic Galdieria sulphuraria (G. sulphuraria) by calcium alginate to improve its affinity to positively charged REEs has been used for simultaneous bioremoval of REEs and ammonium. The results indicate that 97.19%, 96.19%, and 98.87% of La, Y, and Sm, respectively, are removed by G. sulphuraria beads (GS-BDs). The adsorption of REEs by calcium alginate beads (BDs) and GS-BDs is well fitted by both pseudo first-order (PFO) and pseudo second-order (PSO) kinetic models, implying that adsorption of REEs involves both physical adsorption caused by affinity of functional groups such as -COO- and -OH and chemical adsorption based on ion exchange of Ca2+ with REEs. Notably, GS-BDs exhibit high tolerance to La, Y, and Sm with maximum removal efficiencies of 97.9%, 96.6%, and 99.1%, respectively. Furthermore, the ammonium removal efficiency of GS-BDs is higher than that of free G. sulphuraria cells at an initial ammonium concentration of 100 mg L-1, while the efficiency decreases when initial concentration of ammonium is higher than 150 mg L-1. Last, small size of GS-BDs favors ammonium removal because of their lower mass transfer resistance. This study achieves simultaneous removal of REEs and ammonium from acidic mining drainage, providing a potential strategy for biotreatment of REE tailing wastewater.

Compact quartz-enhanced photoacoustic sensor for ppb-level ambient NO2 detection by use of a high-power laser diode and a grooved tuning fork.

A compact quartz-enhanced photoacoustic sensor for ppb-level ambient NO2 detection is demonstrated, in which a high-power blue laser diode module with a small divergence angle was employed to take advantages of the directly proportional relationship between sensitivity and power, hence improving the detection sensitivity. In order to extend the stability time, a custom grooved quartz tuning fork with 800-µm prong spacing is employed to avoid complex signal balance and/or optical spatial filter components. The sensor performance is optimized and assessed in terms of optical coupling, power, gas flow rate, pressure, signal linearity and stability. A minimum detectable concentration (1σ) of 7.3 ppb with an averaging time of 1 s is achieved, which can be further improved to be 0.31 ppb with an averaging time of 590 s. Continuous measurements covering a five-day period are performed to demonstrate the stability and robustness of the reported NO2 sensor system.

Revealing dual roles of g-C3N4 in Chlorella vulgaris cultivation.

Booming graphitic carbon nitride (g-C3N4) photocatalyzed water splitting increases crisis of aquatic contamination. However, a controversial understanding regarding effect of g-C3N4 on growth of microalgae still exists. Accordingly, Chlorella vulgaris were cultured in 0-250 mg/L of g-C3N4 with biomass named as C-0, C-50, C-100, C-150, C-200, and C-250, respectively. g-C3N4 below 200 mg/L was beneficial to short-term cultivation of microalgae, while it was harmful to long-time cultivation. Protein factions of C-0, C-100, and C-250 were 41.4, 42.3, and 36.4 wt%, while their lipid factions varied from 21.5, 16.9, to 17.8 wt%, respectively. In short-term cultivation, superoxide dismutase's activity of C-0, C-150, and C-250 increased dramatically, while accumulated H2O2 led to increased activity of catalase. However, it started to decrease once antioxidant enzymes were per-oxidized, leading to increase of malondialdehyde content. In long-term cultivation, activities of superoxide dismutase, catalase and malondialdehyde content decreased dramatically owning to peroxidation of algae. Scavenger tests with tertiary butanol and triethanolamine implied that·OH was dominate parameter affecting growth of microalgae. This work indicates that g-C3N4 below 200 mg/L is propitious to short-term cultivation of microalgae, while it is bad to long-time cultivation of microalgae, revealing dual rules of g-C3N4 in Chlorella vulgaris cultivation.

Three-dimensional surface-enhanced Raman scattering substrates constructed by integrating template-assisted electrodeposition and post-growth of silver nanoparticles.

Three-dimensional (3D) plasmonic nano-arrays can provide high surface-enhanced Raman scattering (SERS) sensitivity, good spectral uniformity and excellent reproducibility. However, it is still a challenge to develop a simple and efficient method for fabrication of 3D plasmonic nano-arrays with high SERS performance. Here we report a facile approach to construct ordered arrays of silver (Ag) nanoparticles-assembled spherical micro-cavities using polystyrene (PS) sphere template-assisted electrodeposition and post-growth. The electrodeposited small Ag nanoparticles grow into bigger stable nanoparticles during the post-growth process, which could significantly improve the SERS sensitivity. The Ag nanoparticles-assembled 3D micro-cavity array provides much more hotspots in the excitation laser beam-covered volume than the two-dimensional counterpart. The relative standard deviation (RSD) of 612 cm-1 peak of rhodamine 6G (R6G) was calculated to be 8%, and the RSD of the characteristic peak taken from substrates of different batches was less than 10%. The detectable lower concentration as low as 1 fM was achieved for an aqueous solution of R6G. Such SERS substrate also showed high sensitivity to thiram (fungicide) and paraquat (herbicide) in water with limits of detection of 0.067 nM and 2.5 nM respectively. Furthermore, it also demonstrated that SERS detection of pesticide residues on fruits can be realized, showing a potential application in rapid monitoring food safety.