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The stabilization of transition metals as isolated centres with high areal density on suitably tailored carriers is crucial for maximizing the industrial potential of single-atom heterogeneous catalysts. However, achieving single-atom dispersions at metal contents above 2 wt% remains challenging. Here we introduce a versatile approach combining impregnation and two-step annealing to synthesize ultra-high-density single-atom catalysts with metal contents up to 23 wt% for 15 metals on chemically distinct carriers. Translation to a standardized, automated protocol demonstrates the robustness of our method and provides a path to explore virtually unlimited libraries of mono- or multimetallic catalysts. At the molecular level, characterization of the synthesis mechanism through experiments and simulations shows that controlling the bonding of metal precursors with the carrier via stepwise ligand removal prevents their thermally induced aggregation into nanoparticles. The drastically enhanced reactivity with increasing metal content exemplifies the need to optimize the surface metal density for a given application. Moreover, the loading-dependent site-specific activity observed in three distinct catalytic systems reflects the well-known complexity in heterogeneous catalyst design, which now can be tackled with a library of single-atom catalysts with widely tunable metal loadings. Ministry of Education (MOE) J. Lu acknowledges support from MOE grant (R-143-000-B47-114), the Ministry of Education (Singapore) through the Research Centre of Excellence program (Award EDUN C-33-18-279-V12, Institute for Functional Intelligent Materials) and the National University of Singapore Flagship Green Energy Program (R-143-000-A55-646). X.Z. acknowledges support from a Presidential Postdoctoral Fellowship, Nanyang Technological University, Singapore via grant 03INS000973C150. S.M., D.F.A., and J.P.-R. acknowledge funding from the NCCR Catalysis, a National Centre of Competence in Research funded by the Swiss National Science Foundation. Jun Li acknowledges financial support by the National Natural Science Foundation of China (grant number 22033005) and the Guangdong Provincial Key Laboratory of Catalysis (2020B121201002).

Author(s): Wang, Xiaowei; Yang, Yangyuchen; Lai, Chen; Li, Runlai; Xu, Haomin; Tan, Darren HS; Zhang, Kun; Yu, Wei; Fjeldberg, Oeystein; Lin, Ming; Tang, Wei; Meng, Ying Shirley; Loh, Kian Ping | Abstract: Commercialization of the lithium-sulfur battery is hampered by bottlenecks like low sulfur loading, high cathode porosity, uncontrollable Li2 Sx deposition and sluggish kinetics of Li2 S activation. Herein, we developed a densely stacked redox-active hexaazatrinaphthylene (HATN) polymer with a surface area of 302 m2 g-1 and a very high bulk density of ca. 1.60 g cm-3 . Uniquely, HATN polymer has a similar redox potential window to S, which facilitates the binding of Li2 Sx and its transformation chemistry within the bulky polymer host, leading to fast Li2 S/S kinetics. The compact polymer/S electrode presents a high sulfur loading of ca. 15 mgs cm-2 (200-μm thickness) with a low cathode porosity of 41 %. It delivers a high areal capacity of ca. 14 mAh cm-2 and good cycling stability (200 cycles) at electrolyte-sulfur (E/S) ratio of 5 μL mgs -1 . The assembled pouch cell delivers a cell-level high energy density of 303 Wh kg-1 and 392 Wh L-1 .

The construction of conjugated covalent organic frameworks (COFs) with strong C–C bond linkage remains a big challenge. Herein, we report a new strategy by using an oxidative C–C coupling reaction between electron-rich pyrrole rings at a liquid–liquid interface. Two threefold symmetric monomers containing three terminal pyrrole units were tested, and both gave two-dimensional conjugated COF films with good crystallinity. The bipyrrole units in the as-formed COFs are partially doped, which can be reduced to the neutral form by hydrazine and redoped by I2 vapor. The I2-doped films showed high conductivity (1.35 S/m). Meanwhile, the unpaired electrons exhibited moderate interlayer antiferromagnetic coupling.

Rational design and synthesis of catalytically active two-dimensional (2D) materials with an abundance of atomically precise active sites in their basal planes remains a great challenge. Here, we report a ligand exchange strategy to exfoliate bulk [Cu4(OH)6][O3S(CH2)4SO3] cuprate crystals into atomically thin 2D cuprate layers ([Cu2(OH)3]+). The basal plane of 2D cuprate layers contains periodic arrays of accessible unsaturated Cu(II) single sites (2D-CuSSs), which are found to promote efficient oxidative Chan-Lam coupling. Our mechanistic studies reveal that the reactions proceed via coordinatively unsaturated CuO4(II) single sites with the formation of Cu(I) species in the rate-limiting step, as corroborated by both operando experimental and theoretical studies. The robust stability of 2D-CuSSs in both batch and continuous flow reactions, coupled with their recyclability and good performance in complex molecule derivatization, render 2D-CuSSs attractive catalyst candidates for broad utility in fine chemical synthesis.

The ability to precisely engineer the doping of sub-nanometer bimetallic clusters offers exciting opportunities for tailoring their catalytic performance with atomic accuracy. However, the fabrication of singly dispersed bimetallic cluster catalysts with atomic-level control of dopants has been a long-standing challenge. Herein, we report a strategy for the controllable synthesis of a precisely doped single cluster catalyst consisting of partially ligand-enveloped Au4Pt2 clusters supported on defective graphene. This creates a bimetal single cluster catalyst (Au4Pt2/G) with exceptional activity for electrochemical nitrogen (N2) reduction. Our mechanistic study reveals that each N2 molecule is activated in the confined region between cluster and graphene. The heteroatom dopant plays an indispensable role in the activation of N2 via an enhanced back donation of electrons to the N2 LUMO. Moreover, besides the heteroatom Pt, the catalytic performance of single cluster catalyst can be further tuned by using Pd in place of Pt as the dopant., The fabrication of singly dispersed metal cluster catalysts with atomic-level control of dopants is a long-standing challenge. Here, the authors report a strategy for the synthesis of a precisely doped single cluster catalyst which shows exceptional activity for electrochemical dinitrogen reduction.

The ability to tune both local and global environments of a single-metal active center on a support is crucial for the development of highly robust and efficient single-atom electrocatalysts (SAECs...

Molecule-like electrocatalysts with FeN4motifs have been demonstrated to be excellent candidates for various renewable energy conversions. The ability to further tune the electronic properties of molecular FeN4motifs and integrate them onto conductive supports represents a key step towards the synthesis of highly robust and efficient single-atom catalysts (SACs) for practical applications. Here, we developed a new route for the synthesis of a well-defined single-atom FeN4electrocatalystvia in situpolymerization of four amino groups functionalized iron phthalocyanine (NH2-FePc) molecules on conductive carbon nanotubes. The intermolecular oxidative dimerization between the amino groups of NH2-FePc creates the desired electron-withdrawing pyrazine linker between FeN4motifs, which can significantly optimize their electrocatalytic performances. As a result, the FeN4-SAC exhibits both outstanding ORR activity (a half-wave potential of 0.88 Vvs.RHE) and excellent performance in Zn-oxygen batteries, outperforming the commercial Pt/C and pristine iron phthalocyanine (FePc) catalysts. Our theoretical calculations reveal that the presence of electron-withdrawing linkers shifts the occupied antibonding states towards lower energies and thus weakens the Fe-O bond, which is primarily responsible for the enhancement of ORR activity.

Agriculture always plays a crucial role on the world economy, and it is the foundation of rural economy. Especially in China is the developing country which has large population, at the same time it is one of the top agricultural producing country in World. Agricultural development is to guarantee a national food security, at the same time, it is a important measures to narrow the gap between urban and rural areas. This article analyse the challenges that modern economy development in China to face with current situations which including impact of aging population education system high logistics cost, and propose countermeasures to accelerate the development of modern economy and agriculture pointedly.

Tin selenide (SnSe) nanostructures hold great promise as an anode material in lithium-ion batteries (LIBs) due to their high storage capacity, rapid lithiation kinetics and long-term cycling stability. However, a scalable synthesis of SnSe nanostructures with a well-defined size remains a challenge in chemistry. Here, we report cathodic exfoliation of a bulk SnSe crystal for a high-yield (>90%) synthesis of sub-5 nm scale SnSe quantum dots (QDs). As-exfoliated SnSe QDs demonstrate a superior performance as the anode material for LIBs. Our results reveal that SnSe QDs not only accommodate the volume expansion/contraction during the reversible charging/discharging in LIBs but also increase the effective contact interface area between the nanostructured anode materials and electrolyte, leading to a high charging/discharging rate and superior cycling performance. Additionally, SnSe QD based LIBs exhibit a reversible capacity retention of 550 mA h g−1 and high coulombic efficiency approaching 100% after 1500 charging/discharging cycles at a current density of 0.5 A g−1.

Exposing and stabilizing undercoordinated platinum (Pt) sites and therefore optimizing their adsorption to reactive intermediates offers a desirable strategy to develop highly efficient Pt-based electrocatalysts. However, preparation of atomically controllable Pt-based model catalysts to understand the correlation between electronic structure, adsorption energy, and catalytic properties of atomic Pt sites is still challenging. Herein we report the atomically thin two-dimensional PtTe2 nanosheets with well-dispersed single atomic Te vacancies (Te-SAVs) and atomically well-defined undercoordinated Pt sites as a model electrocatalyst. A controlled thermal treatment drives the migration of the Te-SAVs to form thermodynamically stabilized, ordered Te-SAV clusters, which decreases both the density of states of undercoordinated Pt sites around the Fermi level and the interacting orbital volume of Pt sites. As a result, the binding strength of atomically defined Pt active sites to H intermediates is effectively reduced, which renders PtTe2 nanosheets highly active and stable in hydrogen evolution reaction., Precisely regulating Pt catalytic sites is important and challenging. Herein the authors engineer the clustering of single atomic Te vacancies in atomically thin PtTe2 to optimize the electronic structure, adsorption energy, and catalytic performance of atomically defined Pt sites.

Single-atom catalysts (SACs) with magnetic elements as the active center have been widely exploited for efficient electrochemical conversions. Understanding the catalytic role of spin, and thus modulating the spin density of a single-atom center, is of profound fundamental interest and technological impact. Here, we synthesized ferromagnetic single Co atom catalysts on TaS2 monolayers (Co1/TaS2) as a model system to explore the spin-activity correlation for the oxygen evolution reaction (OER). A single Co atom adsorbed at the hollow site (CoHS) with spin-polarized electronic states serves as the active site for OER, whose spin density can be regulated by its neighboring single Co site via tuning the Co loading. Both experimental and theoretical results reveal the spin density-dependent OER activity that an optimal spin density of CoHS can be achieved with a neighboring hetero-single CoTa site (substitution of Ta by Co) for a superior OER performance, in contrast to a homo-single CoHS site, which creates an excessive spin density over vicinal CoHS. An optimized spin density of CoHS results in an optimal binding energy of oxygen species for the OER. Establishing the spin-activity correlation in SACs may create a descriptor for designing efficient magnetic SACs for renewable energy conversions.

Single-atom catalysts (SACs) represent a new frontier in heterogeneous catalysis due to their remarkable catalytic properties and maximized atomic utilization. However, single atoms often bond to the support with polarized electron density and thus exhibit a high valence state, limiting their catalytic scopes in many chemical transformations. Here, we demonstrated that two-dimensional (2D) black phosphorus (BP) act as giant phosphorus (P) ligand to confine a high density of single atoms (eg, Pd1, Pt1) via atomic layer deposition. Unlike other 2D materials, BP with relatively low electronegativity and buckled structure favors the strong confinement of robust zero-valent palladium SACs in the vacancy site. Metallic Pd1/P SAC shows a highly selective semi-hydrogenation of phenylacetylene towards styrene, outperforming high-valence Pt1/P SAC, and also distinct from metallic Pd nanoparticles that facilitate the formation of fully hydrogenated products. Our DFT calculations reveal that Pd atom forms covalent-like bonding with adjacent P atoms, wherein H atoms tend to adsorb over electron-rich region for the subsequent hydrogenation. Zero-valent Pd in the confined space favors a larger energy gain for the synthesis of partially-hydrogenated product over the fully-hydrogenated one. Our work provides a new route towards the synthesis of zero-valent SACs on BP for a wide range of organic transformations.

Like phosphorene, phosphorene nanoribbon (PNR) promises exotic properties but unzipping phosphorene into edge-defined PNR is non-trivial because of uncontrolled cutting of phosphorene along random directions. Here a facile electrochemical strategy to fabricate zigzag-edged PNRs in high yield (>80%) is reported. The presence of chemically active zigzag edges in PNR allows it to spontaneously react with Li to form a Li+ ion conducting Li3 P phase, which can be used as a protective layer on Li metal anode in lithium metal batteries (LMBs). PNR protective layer prevents the parasitic reaction between lithium metal and electrolyte and promotes Li+ ion diffusion kinetics, enabling homogenous Li+ ion flux and long-time cycling stability up to 1100 h at a current density of 1 mA cm-2 . LiFePO4 |PNR-Li full-cell batteries with an areal capacity of 2 mAh cm-2 , a lean electrolyte (20 µl mAh-1 ) and a negative/positive (N/P) electrodes ratio of 3.5 can be stably cycled over 100 cycles.

Cuprous based chalcogenides have attracted intensive research interest due to the potential applications in solar energy conversion. However, typical fabrications of these compounds are often carried out under severe conditions, such as inert gas protection, high vacuum, and/or extreme high temperature. Here we reported a one-pot process for cuprous based chalcogenides synthesis in aqueous solution. A strategy for BiCuSO nanosheets fabrication without toxic chemicals or rigorous reagents at pretty low temperatures under an ambient atmosphere was established, with the practicality of morphology controlling and the compatibility of multifarious precursors. Platelike BiCuSO with a thickness range from several to hundreds nanometers are fabricated by adjusting the alkali concentration, reaction time, and temperature. The positive effect of alkali hydroxide concentration is proposed cautiously based on the experimental results. The photocatalytic activities of BiCuSO nanosheet under UV, visible, and near-infrared irradiation were also investigated. BiCuSO obtained at room temperature with a thickness of 4.5 nm showed the most impressive efficiency to decompose organic contaminants. Our research presented a new way for cuprous sulfides fabrication, and might open up a new vista for large-scale synthesis of cuprous based materials as promising broadband spectrum light-absorbing materials.

In the DV -HOP algorithm of the wireless sensor network, an inaccurate estimation of the minimum hop count and the average hop distance produces a positioning error. Therefore, this paper proposes an improved DV-HOP algorithm. The algorithm reevaluates the average hop distance of the anchor node and corrects the minimum hop count of the node to be located and the anchor node, which reduces the above error. First, the average hop distance of the anchor node closest to the positioned node is reassessed according to the error. Then, the minimum hop count is obtained by the average hop distance of the revaluation, and the correction coefficient of the ratio of the minimum hop count to the actual minimum hop count is obtained, and the minimum hop count of the node to be positioned is corrected by the correction coefficient. Finally, the distance between the node to be located and the anchor node is calculated, and the position of the node to be positioned is calculated by the least squares method. Simulation results show that the improved dv-hop algorithm can reduce the node positioning error and improve the positioning accuracy.

Pure perovskite BiFeO3, sillenite Bi2Fe4O9, and BiFeO3/Bi2Fe4O9 were synthesized facilely by controlling the precursor Bi/Fe ion ratio through a hydrothermal method. The phase composition, morphology, optical properties, and photocatalytic activity of as-prepared samples were investigated in detail. Our results indicate that the morphology and properties of products strongly dependent on the precursor Bi/Fe ion ratio. Photocatalysis of Congo Red reveals that sillenite Bi2Fe4O9 shows superior activity to perovskite BiFeO3, and BiFeO3/Bi2Fe4O9 exhibited higher activity with 71.45% degradation rate in 90 min. It provides an easy and efficient way to tune the composition and photocatalytic activity of Bi-based oxides.

Energy band engineering and the nature of surface/interface of a semiconductor play a significant role in searching high efficiency photocatalysts. Actually, the active facets, morphology controlling, especially the exposed facets modulation of photocatalysts during preparation are very desirable. In order to achieve high photocatalytic performance, intrinsic mechanism of such anisotropic properties should be fully considered. In this review, we mainly emphasis on the latest research developments of several extensively investigated photocatalysts and their anisotropic photocatalytic properties, as well as the correlation between effective masses anisotropy and photocatalytic properties. It will be helpful to understand the photocatalytic mechanism and promote rational development of photocatalyst for wide applications.

Developing active, stable, and low-cost electrocatalysts which can promote the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in the same electrolyte is undoubtedly a vital progress toward a hydrogen economy. Herein, we report that such electrocatalysts can be easily prepared by pyrolyzing a precursor composed of nickel and iron salts with urea under inert atmospheres without any post-treatments. The obtained products are composed of metallic nickel–iron alloy nanoparticles either encapsulated in or dispersed on nitrogen-doped bamboo-like carbon nanotubes (CNTs). This simple synthesis route could simultaneously realize nanostructuring, doping, and hybridizing with nanocarbon, which have been demonstrated as efficient strategies to optimize the catalytic activity of an electrocatalyst. The in situ formed hybrid catalysts exhibit good catalytic performances for both OER and HER under alkaline conditions, and the doping content of iron significantly affects the activities. When the bes...

Ferromagnetism and superconductivity are two antagonistic phenomena since ferromagnetic exchange fields tend to destroy singlet Cooper pairs. Reconciliation of these two competing phases has been achieved in vertically stacked heterostructures where these two orders are confined in different layers. However, controllable integration of these two phases in one atomic layer is a longstanding challenge. Here, an interlayer-space-confined chemical design (ICCD) is reported for the synthesis of dilute single-atom-doped TaS2 molecular superlattice, whereby ferromagnetism is observed in the superconducting TaS2 layers. The intercalation of 2H-TaS2 crystal with bulky organic ammonium molecule expands its van der Waals gap for single-atom doping via co-intercalated cobalt ions, resulting in the formation of quasi-monolayer Co-doped TaS2 superlattices. Isolated Co atoms are decorated in the basal plane of the TaS2 via substituting the Ta atom or anchoring at a hollow site, wherein the orbital-selected p-d hybridization between Co and neighboring Ta and S atoms induces local magnetic moments with strong ferromagnetic coupling. This ICCD approach can be applied to various metal ions, enabling the synthesis of a series of crystal-size TaS2 molecular superlattices.

High efficiency photocatalyst Bi2O2(CO3)1−xSx was synthesized conveniently with chemical bath precipitation using Bi2O2CO3 as the precursor. The microstructures of the samples are systematically characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS) and UV-Vis spectroscopy; the optical and photocatalytic properties are carefully tested as well. The content of S, which was tuned through the controlling of the precipitation process, was verified to have an intense effect over the photocatalytic properties. A nearly saturated S ratio and the best photocatalytic performance were observed in specimens with the most S content. Our study reveals that, with negligible influence of the morphology and crystal structure, Bi2O2(CO3)1−xSx possessed a broadened optical absorption regionfromultraviolet to visible light, and enhanced photocatalytic activity in comparison to precursor Bi2O2CO3 in photocatalytic degradation of Congo Red aqueous solution.

Highly (001)-textured BiFeO

Highly (001)-textured BiFeO3 film in tetragonal phase (T-BFO) with a giant c/a ratio was first obtained on quartz/polycrystalline ITO substrate. Our results indicate that the polycrystalline ITO layer with small surface roughness is a critical point to control the growth of T-BFO structure. It should be ascribed to the fact that a Bi-rich phase interlayer (∼5 nm) could be formed on ITO, which acted as a crystal seed layer and thus induced the growth of (001)-textured T-BFO structure. The observed weak room temperature ferromagnetism should be attributed to Fe valence change. Open circuit potential measurements under 360 μW/cm2 full spectra irradiation show that the open circuit potential and the lifetime of photo-induced carriers increased under applied magnetic field, which reveals that the applied magnetic field can manipulate the photo electrochemical behaviors of BFO film. Our findings offer a simple way to fabricate highly (001)-textured T-BFO film, which make it desirable to obtain extensive applica...

Electrochemical reduction of carbon dioxide with renewable energy is a sustainable way of producing carbon-neutral fuels. However, developing active, selective and stable electrocatalysts is challenging and entails material structure design and tailoring across a range of length scales. Here we report a cobalt-phthalocyanine-based high-performance carbon dioxide reduction electrocatalyst material developed with a combined nanoscale and molecular approach. On the nanoscale, cobalt phthalocyanine (CoPc) molecules are uniformly anchored on carbon nanotubes to afford substantially increased current density, improved selectivity for carbon monoxide, and enhanced durability. On the molecular level, the catalytic performance is further enhanced by introducing cyano groups to the CoPc molecule. The resulting hybrid catalyst exhibits >95% Faradaic efficiency for carbon monoxide production in a wide potential range and extraordinary catalytic activity with a current density of 15.0 mA cm−2 and a turnover frequency of 4.1 s−1 at the overpotential of 0.52 V in a near-neutral aqueous solution., Electrochemical reduction of carbon dioxide is a sustainable way of producing carbon-neutral fuels. Here, the authors take a combined nanoscale and molecular approach to develop a highly active and selective cobalt phthalocyanine/carbon nanotube hybrid electrocatalyst for carbon dioxide reduction to carbon monoxide.

With the constant improvement of Wireless Sensor Network, its application scenarios become more diverse. Due to the limited resources of sensor nodes, there are many researches devoted to the optimization of network structure and the prolongation of network life. The proposed extended protocol is based on the chain-based routing technique of PEGASIS. In a newly deployed network, intra-group trust is formed through the Group Authentication based on Merkle Tree, which can protect the node information and resist the deception of false message. In the steady phase, the whole network re-chain is replaced by re-chain within the group when any node dies. Simulation results show that the scheme proposed in this paper has obvious improvement in terms of residual energy and network life compared with PEGASIS.

When designing wastewater aeration systems, fine-pore diffusers are typically selected for their potential energy efficiency. Because aeration is one of the most energy-intensive unit operations during treatment, the accurate quantification of aeration performance parameters is crucial to minimize the process energy footprint. Oxygen transfer efficiency in process water is the key design parameter; however, performance indicators that account for fouling and increased pressure drop with time must be considered. Both fouling and pressure drop increase cause an increase in blower power requirements. This paper presents a new approach to improve this design procedure, without altering the technical structure of the classical approach. Although the administrative and bidding milestones are underway (i.e., in the first few months of the project), an independent aeration team can test candidate diffusers suitable for design in an in situ aeration column. Subsequently, an extended fouling test in the pla...

Pure BiFeO3 and heterostructured BiFeO3/BiFe0.95Mn0.05O3 (5% Mn-doped BiFeO3) thin films have been prepared by a chemical deposition method. The band structures and photosensitive properties of these films have been investigated elaborately. Pure BiFeO3 films showed stable and strong response to photo illumination (open circuit potential kept −0.18 V, short circuit photocurrent density was −0.023 mA·cm−2). By Mn doping, the energy band positions shifted, resulting in a smaller band gap of BiFe0.95Mn0.05O3 layer and an internal field being built in the BiFeO3/BiFe0.95Mn0.05O3 interface. BiFeO3/BiFe0.95Mn0.05O3 and BiFe0.95Mn0.05O3 thin films demonstrated poor photo activity compared with pure BiFeO3 films, which can be explained by the fact that Mn doping brought in a large amount of defects in the BiFe0.95Mn0.05O3 layers, causing higher carrier combination and correspondingly suppressing the photo response, and this negative influence was more considerable than the positive effects provided by the band modulation.

Photocatalysis is attracting enormous interest driven by the great promise of addressing current energy and environmental crises by converting solar light directly into chemical energy. However, efficiently harvesting solar energy for photocatalysis remains a pressing challenge and the charge kinetics and mechanism of the photocatalytic process is far from being well understood. Here we report a new full solar spectrum driven photocatalyst in the system of a layered oxyselenide BiCuSeO with good photocatalytic activity for degradation of organic pollutants and chemical stability under light irradiation and the photocatalytic performance of BiCuSeO can be further improved by band gap engineering with introduction of La. Our measurements and density-functional-theory calculations reveal that the effective mass and mobility of the carriers in BiCuSeO can be tuned by the La-doping, which are responsible for the tunable photocatalytic activity. Our findings may offer new perspectives for understanding the mechanism of photocatalysis through modulating the charge mobility and the effective mass of carriers and provide a guidance for designing efficient photocatalyts.

Amoxicillin is a widely used antibiotic and has been detected in natural waters. Its environmental fate is in part determined by hydrolysis, and, direct and indirect photolysis. The hydrolysis rate in distilled water and water to which five different isolated of dissolved organic matter (DOM) was added, were evaluated. In the five different DOM solutions hydrolysis accounted for 5-18% loss of amoxicillin. Direct and indirect photolysis rates were determined using a solar simulator and it appeared that indirect photolysis was the dominant loss mechanism. Direct photolysis, in a solar simulator, accounted for 6-21% loss of amoxicillin in the simulated natural waters. The steady-state concentrations of singlet oxygen, (1)ΔO(2) (∼10(-13) M) and hydroxyl radical, •OH (∼10(-17) M) were obtained in aqueous solutions of five different dissolved organic matter samples using a solar simulator. The bimolecular reaction rate constant of (1)ΔO(2) with amoxicillin was measured in the different solutions, k(ΔO(2)) = 1.44 × 10(4) M(-1) s(-1). The sunlight mediated amoxicillin loss rate with (1)ΔO(2) (∼10(-9) s(-1)), and with •OH (∼10(-7) s(-1)), were also determined for the different samples of DOM. While (1)ΔO(2) only accounted for 0.03-0.08% of the total loss rate, the hydroxyl radical contributed 10-22%. It appears that the direct reaction of singlet and triplet excited state DOM ((3)DOM(∗)) with amoxicillin accounts for 48-74% of the loss of amoxicillin. Furthermore, the pseudo first-order photodegradation rate showed a positive correlation with the sorption of amoxicillin to DOM, which further supported the assumption that excited state DOM∗ plays a key role in the photochemical transformation of amoxicillin in natural waters. This is the first study to report the relative contribution of all five processes to the fate of amoxicillin in aqueous solution.

High efficiency photocatalyst Bi2O2(CO3)1−xSx was synthesized conveniently with chemical bath precipitation using Bi2O2CO3 as the precursor. The microstructures of the samples are systematically characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS) and UV-Vis spectroscopy; the optical and photocatalytic properties are carefully tested as well. The content of S, which was tuned through the controlling of the precipitation process, was verified to have an intense effect over the photocatalytic properties. A nearly saturated S ratio and the best photocatalytic performance were observed in specimens with the most S content. Our study reveals that, with negligible influence of the morphology and crystal structure, Bi2O2(CO3)1−xSx possessed a broadened optical absorption regionfromultraviolet to visible light, and enhanced photocatalytic activity in comparison to precursor Bi2O2CO3 in photocatalytic degradation of Congo Red aqueous solution.

We engineered various orientations of NiO layers for NiO-based heterostructures (NiO/Au/STO) to investigate their effects on the generation of hot electrons and holes. Our calculation and experimental results suggested that bandgap engineering and the orientation of the hole transport layer (NiO) were crucial elements for the optimization of photoelectric responses. The (100)-orientated NiO/Au/STO achieved the highest photo-current density (∼30 μA/cm2) compared with (111) and (110)-orientated NiO films, which was attributed to the (100) films's lowest effective mass of photogenerated holes (∼1.82 m0) and the highest efficiency of separating and transferring electron-holes of the (100)-orientated sample. Our results opened a direction to design a high efficiency photoelectric solar cell.We engineered various orientations of NiO layers for NiO-based heterostructures (NiO/Au/STO) to investigate their effects on the generation of hot electrons and holes. Our calculation and experimental results suggested that bandgap engineering and the orientation of the hole transport layer (NiO) were crucial elements for the optimization of photoelectric responses. The (100)-orientated NiO/Au/STO achieved the highest photo-current density (∼30 μA/cm2) compared with (111) and (110)-orientated NiO films, which was attributed to the (100) films's lowest effective mass of photogenerated holes (∼1.82 m0) and the highest efficiency of separating and transferring electron-holes of the (100)-orientated sample. Our results opened a direction to design a high efficiency photoelectric solar cell.

In view of the discrepancy in the literature with regard to the structure of Fe(3 1 0), we have investigated this surface by a refined quantitative LEED analysis and a pseudopotential DFT study. Similar results to a previous LEED analysis have been obtained by our new LEED analysis. Our pseudopotential calculations have reproduced the relaxation sequence of the interlayer spacings determined by our LEED analysis, i.e., − + − + with the largest discrepancy in the structural parameters less than 0.04 A. A large lateral relaxation of the interlayer registry between the first and second layers has been confirmed by our LEED analysis and pseudopotential calculations.

We demonstrate in this study that nanofibres containing Co (or Fe, Ni), SrO and trace carbon can be synthesized via a catalytic process using CH4 or C2H4 as the reaction gas. The synthesized nanofibres are 50–200 nm in diameter and 1–15 µm in length. The length of the fibres can be controlled via a change of the reaction temperature. The formation mechanism is likely to be a two-step process combining catalytic decomposition of a carbon-containing gas and a sequential self-assembly process of growth into nanofibres.

Developing earth-abundant, active, and stable electrocatalysts for water splitting is a vital but challenging step for realizing efficient conversion and storage of sustainable energy. Here, a multiscale structure-engineering approach to construct iron (Fe) doped cobalt monophosphide (CoP) hybrids for efficient electrocatalysis of water splitting is reported. A two-step method is developed to synthesize CoP nanosheets with uniform Fe doping and hybridization with carbon nanotubes (CNTs). The nanostructuring, uniform doping, and hybridization with CNT afford efficient electrocatalysts comparable to Pt/C for hydrogen evolution reactions in acidic, neutral, and alkaline electrolytes. It is found that the Fe doping level has different effects on catalytic activities in different electrolytes. Furthermore, after in situ oxidization/hydrolysis of the phosphides to corresponding oxyhydroxides, the hybrid electrocatalysts exhibit better performances than the benchmark commercial Ir/C for catalyzing the oxygen evolution reaction. A two-electrode alkaline water electrolyzer constructed with these hybrid electrocatalysts can afford a current density of 10 mA cm−2 at a voltage of 1.5 V.

Chemical Enhanced Oil Recovery (EOR) has regained its attention because of high oil price and the depletion of conventional oil reservoirs. This process is more complex than the primary and secondary recovery and requires detailed engineering design for a successful field-scale application. An alkaline/co-solvent/polymer (ACP) formulation was developed and corefloods were performed for a cost efficient alternative to alkaline/surfactant/polymer floods. Alkali reacts with acidic components of heavy oil (i.e. 170 cp in-situ viscosities) to form natural soap and significantly reduce the interfacial tension, which allows producing residual oil not contacted by waterflood or polymer flood alone. Polymer provides mobility control to drive chemical slug and oil bank. Co-solvent helps to improve the compatibility between in-situ soap and polymer and to reduce microemulsion viscosity. An impressive recovery of 70% of the waterflood residual oil saturation was achieved from an outcrop core where the remaining oil saturation after the ACP flood was reduced to only 13.5%. The results were promising with very low chemical utilization. UTCHEM reservoir simulator was used to model the coreflood experiment to obtain parameters for pilot scale simulations. Geological model was based on unconsolidated reservoir sand with multiple seven spot well patterns. However, facility capacity and field logistics, reservoir heterogeneity as well as mixing and dispersion effects might prevent the design followed in coreflood to be directly scaled for field implementation. Field-scale sensitivity simulations were conducted to optimize the design. The influence of chemical mass, slug size, polymer pre-flush, and injection rates on ultimate oil recovery was investigated. This research emphasizes the importance of small well spacing and good mobility control on recovery efficiency. The in-situ soap generated from alkali-naphthenic acid reaction not only mobilizes residual oil to increase oil recovery, but also enhances water relative permeability to increase injectivity. The paper discusses a cost effective chemical flooding design with an impressive oil recovery by adding relatively small solvent and polymer quantities to injected water. The potential for producing residual oil of the viscous oil is demonstrated in both the coreflood and pilot-scale simulations.

Beta-blockers, prescribed for the treatment of high blood pressure and for long-term use after a heart attack, have been detected in surface and ground waters. This study examines the photochemical fate of three beta-blockers, atenolol, metoprolol, and nadolol. Hydrolysis accounted for minor losses of these beta-blockers in the pH range 4–10. The rate of direct photolysis at pH 7 in a solar simulator varied from 6.1 to 8.9 h − 1 at pH 7. However, the addition of a natural organic matter (NOM) isolate enhanced the photochemical loss of all three compounds. Indirect photochemical fate, generally described by reactions with hydroxyl radical ( OH) and singlet oxygen ( 1 ΔO 2 ), and, the direct reaction with the triplet excited state, 3 NOM ⁎ , also varied but collectively appeared to be the major loss factor. Bimolecular reaction rate constants of the three beta-blockers with 1 ΔO 2 and OH were measured and accounted for 0.02–0.04% and 7.2–38.9% of their loss, respectively. These data suggest that the 3 NOM ⁎ contributed 50.6–85.4%. Experiments with various 3 NOM ⁎ quenchers supported the hypothesis that it was singly the most important reaction. Atenolol was chosen for more detailed investigation, with the photoproducts identified by LC–MS analysis. The results suggested that electron-transfer could be an important mechanism in photochemical fate of beta-blockers in the presence of NOM.

Single phase polycrystalline BiFeO3 thin films were grown on three different substrates via chemical solution deposition. Our results indicate that the band gap of as-prepared BiFeO3 films can be tuned (2.02–2.67 eV) by the grain size effects caused by the substrates. These BiFeO3 films show good photocatalytic properties by the degradation of Congo red solution under visible-light irradiation ( λ > 400 nm). Additionally, weak ferromagnetic behaviors can be observed at room temperature in all the films, which should be correlated to the destruction of the incommensurate cycloid spin structure of BiFeO3 phase and the coexistence of Fe3+ and Fe2+ as confirmed by X-ray photoelectron spectroscopy.