Building Fe atom–cluster composite sites using a site occupation strategy to boost electrochemical oxygen reduction

The high-temperature pyrolysis process for preparing M–N–C single-atom catalyst usually results in high heterogeneity in product structure concurrently contains multiscale metal phases from single atoms(SAs),atomic clusters to nanoparticles.Therefore,understanding the interactions among these components,especially the synergistic effects between single atomic sites and cluster sites,is crucial for improving the oxygen reduction reaction(ORR)activity of M–N–C catalysts.Accordingly,herein,we constructed a model catalyst composed of both atomically dispersed FeN4 SA sites and adjacent Fe clusters through a site occupation strategy.We found that the Fe clusters can optimize the adsorption strength of oxygen reduction intermediates on FeN4 SA sites by introducing electron-withdrawing–OH ligands and decreasing the d-band center of the Fe center.The as-developed catalyst exhibits encouraging ORR activity with halfwave potentials(E1/2)of 0.831 and 0.905 V in acidic and alkaline media,respectively.Moreover,the catalyst also represents excellent durability exceeding that of Fe–N–C SA catalyst.The practical application of Fe(Cd)–CNx catalyst is further validated by its superior activity and stability in a metalair battery device.Our work exhibits the great potential of synergistic effects between multiphase metal species for improvements of singleatom site catalysts.

Heterostructured Pt-Ni_(3)Mo_(3)N formed via ammonia-containing polyoxometalates for highly efficient electrocatalytic hydrogen evolution in acid medium

Constructing heterostructured nanohybrid is considered as a prominent route to fabricate alternative electrocatalysts to commercial Pt/C for hydrogen evolution reaction(HER).In this work,(NH_(4))_(4)[NiH_(6)Mo_(6)O_(4)]·5H_(2)O polyoxometalates(NiMo_(6))are adopted as the cluster precursors for simple fabrication of heterostructured Pt-Ni_(3)Mo_(3)N nanohybrids supported by carbon black(Pt-Ni_(3)Mo_(3)N/C)without using additional N sources.The improved porosity and enhanced electronic interaction of Pt-Ni_(3)Mo_(3)N/C should be attributed to the integration of Pt with NiMo_(6),which favors the mass transport,promotes the formation of exposed catalytic sites,and benefits the regulation of intrinsic activity.Thus,the as-obtained Pt-Ni_(3)Mo_(3)N/C exhibits impressive and durable HER performance as indicated by the low overpotential of 13.7 mV at the current density of 10 mA cm^(-2) and the stable overpotential during continuous working at 100 mA cm^(-2) for 100 h.This work provides significant insights for the synthesis of new highly active heterostructured electrocatalysts for renewable energy devices.

Molecule aging induced by electron attacking

Here we propose a new concept of"molecule aging":with some special treatment,a molecule could be"aged"by losing some unknown tiny particles or pieces from atoms in the molecule,Such"aging"or loss of unknown tiny particles does not change apparently its molecular structure or chemical composition,but some physicochemical properties could be changed irreversibly.We further confirm such"molecule aging"via a long-term electron attacking to age water(H_(2)O)molecules.The IR spectra show no structural difference between the fresh water and the aged one,while the NMR spectra show that the electron attacking can decrease the size of water clusters.Such facts indicate that the electron attacking indeed can"affect"the structure of water molecule slightly but without damaging to its basic molecule frame.Further exploration reveals that the hydrogen evolution reaction(HER)activity of the aged water molecule is lower than the fresh water on the same Pt/C electrocatalyst.The density functional theory calculations indicate that the shortened O-H bond in H_(2)O indeed can present lower HER activity,so the observed size decrease of water clusters from NMR probably could be attributed to the shortening of O-H bond in water molecules.Such results indicate significantly that the molecule aging can produce materials with new functions for new possible applications.

The decisive role of adsorbed OH^(*)in low‐potential CO electro‐oxidation on single‐atom catalytic sites

CO impurity-induced catalyst deactivation has long been one of the biggest challenges in proton-exchange membrane fuel cells,with the poisoning phenomenon mainly attributed to the overly strong adsorption on the catalytic site.Here,we present a mechanistic study that overturns this understanding by using Rh-based single-atom catalysis centers as model catalysts.We precisely modulated the chelation structure of the Rh catalyst by coordinating Rh with C or N atoms,and probed the reaction mechanism by surface-enhanced Raman spectroscopy.Direct spectroscopic evidence for intermediates indicates that the reactivity of adsorbed OH^(*),rather than the adsorption strength of CO^(*),dictates the CO electrocatalytic oxidation behavior.The RhN_(4)sites,which adsorb the OH^(*)intermediate more weakly than RhC4 sites,showed prominent CO oxidation activity that not only far exceeded the traditional Pt/C but also the RhC4 sites with similar CO adsorption strength.From this study,it is clear that a paradigm shift in future research should be considered to rationally design high-performance CO electro-oxidation reaction catalysts by sufficiently considering the water-related reaction intermediate during catalysis.

Cooperative Caching Strategy Based on Two-Layer Caching Model for Remote Sensing Satellite Networks

In Information Centric Networking(ICN)where content is the object of exchange,in-network caching is a unique functional feature with the ability to handle data storage and distribution in remote sensing satellite networks.Setting up cache space at any node enables users to access data nearby,thus relieving the processing pressure on the servers.However,the existing caching strategies still suffer from the lack of global planning of cache contents and low utilization of cache resources due to the lack of fine-grained division of cache contents.To address the issues mentioned,a cooperative caching strategy(CSTL)for remote sensing satellite networks based on a two-layer caching model is proposed.The two-layer caching model is constructed by setting up separate cache spaces in the satellite network and the ground station.Probabilistic caching of popular contents in the region at the ground station to reduce the access delay of users.A content classification method based on hierarchical division is proposed in the satellite network,and differential probabilistic caching is employed for different levels of content.The cached content is also dynamically adjusted by analyzing the subsequent changes in the popularity of the cached content.In the two-layer caching model,ground stations and satellite networks collaboratively cache to achieve global planning of cache contents,rationalize the utilization of cache resources,and reduce the propagation delay of remote sensing data.Simulation results show that the CSTL strategy not only has a high cache hit ratio compared with other caching strategies but also effectively reduces user request delay and server load,which satisfies the timeliness requirement of remote sensing data transmission.

Copper-Catalyzed C-C(O)C Bond Cleavage of Monoalkylated β-Diketone: Synthesis of α,β-Unsaturated Ketones

A new and simple route for the synthesis of α,β-unsaturated ketones via cleavage of the C-C(O)C single bond of monoalkylated β-diketone has been described. The reaction was catalyzed by copper, a cheap transition metal in a weakly basic medium (K3PO4) at room temperature. To carry out this study, we first had to synthesize the monoalkylated β-diketones 1. Afterwards, α,β-unsaturated ketones 2 were obtained with high yields around 80%. Finally, all the products were characterized by 1H NMR, 13C NMR, and HRMS spectra. .

Key role of electron accessibility at the noble metal-free catalytic interface in hydrogen evolution reaction

The reactant concentration at the catalytic interface holds the key to the activity of electrocatalytic hydrogen evolution reaction(HER),mainly referring to the capacity of adsorbing hydrogen and electron accessibility.With hydrogen adsorption free energy(ΔGH)as a reactivity descriptor,the volcano curve based on Sabatier principle is established to evaluate the hydrogen evolution activity of catalysts.However,the role of electron as reactant received insufficient attention,especially for noble metal-free compound catalysts with poor conductivity,leading to cognitive gap between electronic conductivity and apparent catalytic activity.Herein we successfully construct a series of catalyst models with gradient conductivities by regulating molybdenum disulfide(MoS_(2))electronic bandgap via a simple solvothermal method.We demonstrate that the conductivity of catalysts greatly affects the overall catalytic activity.We further elucidate the key role of intrinsic conductivity of catalyst towards water electrolysis,mainly concentrating on the electron transport from electrode to catalyst,the electron accumulation process at the catalyst layer,and the charge transfer progress from catalyst to reactant.Theoretical and experimental evidence demonstrates that,with the enhancement in electron accessibility at the catalytic interface,the dominant parameter governing overall HER activity gradually converts from electron accessibility to combination of electron accessibility and hydrogen adsorbing energy.Our results provide the insight from various perspective for developing noble metal-free catalysts in electrocatalysis beyond HER.

单组份湿固化异氰酸酯胶黏剂压制桦木集成材的研究

通过聚乙二醇(600)为增链剂、邻苯二甲酸丁酯等为溶剂以及60℃油浴的温度为最佳实验参数,制备出单组份湿固化异氰酸酯胶黏剂,以此胶黏剂压制桦木集成材,蒸煮、干燥后进行压缩剪切强度的测试,得到影响主次关系为增链剂>温度>溶剂,此时做出的试件压剪强度达到7.4MPa,远远超过国标当中对结构集成材压剪强度大于5.9MPa的要求。

Characteristics and Cause Analysis of Heavy Haze in Changchun City in Northeast China

Northeast China has been reported as having serious air pollution in China with increasing occurrences of severe haze episodes. Changchun City, as the center of Northeast China, has longstanding industry and is an important agricultural base. Additionally, Changchun City has a long winter requiring heating of buildings emitting pollution into the air. These factors contribute to the complexity of haze pollution in this area. In order to analyze the causes of heavy haze, surface air quality has been monitored from 2013 to 2015. By using satellite and meteorological data, atmospheric pollution status, spatio-temporal variations and formation have been analyzed. Results indicated that the air quality in 88.9% of days exceeding air quality index(AQI) level-1 standard(AQI >50) according to the National Ambient Air Quality Standard(NAAQS) of China. Conversely, 33.7% of the days showed a higher level with AQI > 100. Extreme haze events(AQI > 300) occurred frequently during agricultural harvesting period(from October 10 to November 10), intensive winter heating period(from Late-December to February) and period of spring windblown dust(April and May). Most daily concentrations of gaseous pollutants, i.e., NO_2(43.8 μg/m^3), CO(0.9 mg/m^3), SO_2(37.9 μg/m^3), and O_3(74.9 μg/m^3) were evaluated within level-1 concentration limits of NAAQS standards. However, particulate matter(PM_(2.5) and PM10) concentrations(67.3 μg/m^3 and 115.2 μg/m^3, respectively) were significantly higher than their level-1 limits. Severe haze in spring was caused by offsite transported dust and windblown surface soil. Heavy haze periods during fall and winter were mainly formed by intensive emissions of atmospheric pollutants and steady weather conditions(i.e., low wind speed and inversion layer). The overlay emissions of widespread straw burning and coal combustion for heating were the dominant factors contributing to haze in autumn, while intensive coal burning during the coldest time was the primary component of total emissions. In addition, general emissions including automobile exhaust, road and construction dust, residential and industrial activities, have significantly increased in recent years, making heavy haze a more frequent occurrence. Therefore, both improved technological strategies and optimized pollution management on a regional scale are necessary to minimize emissions in specified seasons in Changchun City, as well as comprehensive control measures in Northeast China.

Recent development of methanol electrooxidation catalysts for directmethanol fuel cell

Direct methanol fuel cells （DMFCs） are very promising power source for stationary and portable miniatureelectric appliances due to its high efficiency and low emissions of pollutants. As the key material, cata-lysts for both cathode and anode face several problems which hinder the commercialization of DMFCs.In this review, we mainly focus on anode catalysts of DMFCs. The process and mechanism of methanolelectrooxidation on Pt and Pt-based catalysts in acidic medium have been introduced. The influences ofsize effect and morphology on electrocatalytic activity are discussed though whether there is a size effectin MOP, catalyst is under debate. Besides, the non Pt catalysts are also listed to emphasize though Pt isstill deemed as the indispensable element in anode catalyst of DMFCs in acidic medium. Different cata-lyst systems are compared to illustrate the level of research at present. ome debates need to be verifiedwith experimental evidences.

Denitrifying phosphorous removal in anaerobic/anoxic SBR system with different startup operation mode

To achieve stable and efficient nitrogen and phosphorus removal and to investigate the characteristics of the A/A SBR enriched with denitrifying phosphorus removal bacteria(DPB),the whole course of startup was studied with two reactors operated in different mode.The reactor I was operated under anaerobic/settling/anoxic/settling mode,and the reactor II was operated under anaerobic/anoxic/settling mode.Differences between the two reactors in removal efficiency of COD,nitrogen and phosphorus were examined.The results indicated that efficient performance could be achieved in both reactors with different startup operation mode,while the phosphorus removal efficiency was improved sooner in reactor I than in reactor II,which suggested that reactor I would supply a more favorable condition for DPB proliferation.Meanwhile,it was observed that the amount of organic substrates consumption had a linear correlation to that of phosphorus release in anaerobic phase when DPB was accumulated in the A/A SBR denitrifying phosphorus removal system.

Low-temperature synthesis of nitrogen doped carbon nanotubes as promising catalyst support for methanol oxidation

The electrochemical methanol oxidation reaction(MOR) is of paramount importance for direct methanol fuel cell(DMFC) application, where efficient catalysts are required to facilitate the complicated multiple charge transfer process. The catalyst support not only determines the dispersion status of the catalysts particles, but also exerts great influence on the electronic structure of the catalysts, thereby altering its intrinsic activity. Herein, we demonstrated that nitrogen atoms, assisted by the pre-treatment of carbon matrix with oxidants, can be easily doped into carbon nanotubes at low temperature. The obtained nitrogen-doped carbon nanotubes can effectively improve the dispersion of the supported platinum nanoparticles and facilitate the MOR by modifying the electronic structure of platinum atoms,through catalyst-support interaction.

Impacts of Land Cover Changes on Ecosystem Carbon Stocks Over the Transboundary Tumen River Basin in Northeast Asia

Understanding the effects of land cover changes on ecosystem carbon stocks is essential for ecosystem management and environmental protection, particularly in the transboundary region that has undergone marked changes. This study aimed to examine the impacts of land cover changes on ecosystem carbon stocks in the transboundary Tumen River Basin(TTRB). We extracted the spatial information from Landsat Thematic Imager(TM) and Operational Land Imager(OLI) images for the years 1990 and 2015 and obtained convincing estimates of terrestrial biomass and soil carbon stocks with the InVEST model. The results showed that forestland, cropland and built-up land increased by 57.5, 429.7 and 128.9 km2, respectively, while grassland, wetland and barren land declined by 24.9, 548.0 and 43.0 km2, respectively in the TTRB from 1990 to 2015. The total carbon stocks encompassing aboveground, belowground, soil and litter layer carbon storage pools have declined from 831.48 Tg C in 1990 to 831.42 Tg C in 2015 due to land cover changes. In detail, the carbon stocks decreased by 3.13 Tg C and 0.44 Tg C in Democratic People's Republic of Korea(North Korea) and Russia, respectively, while increased by 3.51 Tg C in China. Furthermore, economic development, and national policy accounted for most land cover changes in the TTRB. Our results imply that effective wetland and forestland protection policies among China, North Korea, and Russia are much needed for protecting the natural resources, promoting local ecosystem services and regional sustainable development in the transnational area.

Trace determination and characterization of ginsenosides in rat plasma through magnetic dispersive solid-phase extraction based on core-shell polydopamine-coated magnetic nanoparticles

Enrichment of trace bioactive constituents and metabolites from complex biological samples is challenging.This study presented a one-pot synthesis of magnetic polydopamine nanoparticles(Fe3O4@-SiO2@PDA NPs)with multiple recognition sites for the magnetic dispersive solid-phase extraction(MDSPE)of ginsenosides from rat plasma treated with white ginseng.The extracted ginsenosides were characterized by combining an ultra-high-performance liquid chromatography coupled to a highresolution mass spectrometry with supplemental UNIFI libraries.Response surface methodology was statistically used to optimize the extraction procedure of the ginsenosides.The reusability of Fe3O4@-SiO2@PDA NPs was also examined and the results showed that the recovery rate exceeded 80%after recycling 6 times.Furthermore,the proposed method showed greater enrichment efficiency and could rapidly determine and characterize 23 ginsenoside prototypes and metabolites from plasma.In comparison,conventional methanol method can only detect 8 ginsenosides from the same plasma samples.The proposed approach can provide methodological reference for the trace determination and characterization of different bioactive ingredients and metabolites of traditional Chinese medicines and food.

Surface interaction between Pd and nitrogen derived from hyperbranched polyamide towards highly effective formic acid dehydrogenation

Hydrogen production from formic acid decomposition(FAD)is a promising means of hydrogen energy storage and utilization in fuel cells.Development of efficient catalysts for dehydrogenation of formic acid is a challenging topic.The surface chemical and electronic structure of the active catalysis components is important in formic acid decomposition at room-temperature.Here,the pyrdinic-nitrogen doped catalysts from hyperbranched polyamide were prepared via in situ polymerization reaction process by using activated carbon as a support.Because of the introduction of the polymer,the particles of the catalysts were stabilized,and the average particle diameter was only 1.64 nm.Under mild conditions,the catalysts activities were evaluated for FAD.The optimized Pd-N30/C catalyst exhibited high performance achieving almost full conversion,with a turnover frequency of 3481 h^-1 at 30℃.

Synthesis of polyurea from 1,6-hexanediamine with CO_2 through a two-step polymerization

Activation and transformation of CO_2 is one of the important issues in the field of green and sustainable chemistry. Herein, CO_2 as a carbonoxygen resource was converted to CO_2-polyurea with 1,6-hexanediamine through a two-step polymerization. The reaction parameters such as temperature, pressure and reaction time were examined; and several kinds of catalysts were screened in the absence and presence of NMP solvent. The formed oligomer and the final polyurea were characterized by FT-IR, VT-DRIFTS, NMR, XRD, AFM and their thermal properties were examined by TGA and DSC. It was confirmed that the final polyurea has a high thermal stability; the melting temperature is 269℃ and the decomposition temperature is above 300℃. It is a brittle polymer with a tensile strength of 18.35 MPa at break length of 1.64%. The polyurea has a stronger solvent resistance due to the ordered hydrogen bond in structure. The average molecular weight should be enhanced in the postpolymerization as the appearance, hydrogen bond intensity, crystallinity, melting point and the thermal stability changed largely compared to the oligomer. The present work provides a new kind of polyurea, it is expected to have a wide application in the field of polymer materials.

Highly active PtAu alloy surface towards selective formic acid electrooxidation

The electrochemical oxidation of formic acid has been attracting significant attention in the past few years due to the great potential prospect of direct formic acid fuel cell (DFAFC) in applications, including high theoretical open circuit potential (1.48 V), low fuel crossover, high practical power densities at low temperature, facilitating of proton transport in catalyst layers and low toxicity [1-5].

Effect and Cost Research for Leachate Treatment in PAC/Fenton and Fenton/PAC Technology

To compare the treatment effects and the costs of coagulation/Fenton process and Fenton/coagulation process in leachate treatment,fresh and old leachates were respestively treated with these two techniques.The experimental results indicate that the highest chemical oxygen demand(COD)removal rate of Fenton reaction on leachate can be acquired under the conditions of pH=3.5,nH2O2/nFe2+=6,mH2O2/mCOD=3,and reaction time=4 h.Polyaluminium chloride(PAC)coagulation has the highest COD removal rate on leachate under the condition of mPAC/mCOD=0.6.Under the optimum reaction conditions,coagulation/Fenton and Fenton/coagulation processes were respestively adopted to treat raw leachate.The data also show that COD removal rate of coagulation/Fenton process on fresh and old leachates are 90.56% and 86.52% respectively and that of Fenton/coagulation process 89.99% and 85.99%,so there is no obvious difference.But the cost of coagulation/Fenton process for leachate treatment is RMB 62.6,lower than that of Fenton/coagulation process.Therefore,coagulation/Fenton process is more optimized than Fenton/coagulation process for leachate treatment.

Engineering the HER catalytic behavior of heteroatom-doped molybdenum disulfide via versatile partial cation exchange

Water electrolysis is regarded as an environmental friendly and effective technique for large-scale hydrogen(H2)production[1,2].To date,Pt-based electrocatalysts are still the most efficient HER catalysts[3].However,the prohibitive cost and scarcity of precious metal catalysts have restricted its large-scale applications.Thus,finding an earth-abundant and effective alternative electrocatalysts is crucial to the development of‘hydrogen economy'.

Electrocatalytic water splitting at nitrogen-doped carbon layers-encapsulated nickel cobalt selenide

Generally,the catalytic overpotentials of hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)are unavoidable because of the low charge transfer.In this work,two strategies of alloying of Co with Ni and enclosing of electrocatalysts with carbonaceous materials were both used to accelerate the catalytic efficiency of cobalt selenide for water splitting.The nitrogen-doped carbon(NC)layer improves the reaction kinetics by efficient charge transfer.The alloying of metal into composited electrocatalysts can modify the electronic properties of host materials,thereby tuning the adsorption behavior of intermediate and improving the electrocatalytic activity.As expected,Nyquist plots reveal that the charge-transfer resistance(Rct)of nickel cobalt selenide encapsulated into nitrogen-doped carbon layer(CoNiSe/NC-3,Co:Ni=1:1)are just 5 and 9 for HER and OER,respectively,which are much lower than those of CoSe/NC-1(Co:Ni=1:0)(81 and 138)and CoNiSe/NC-3 without NC(CoNiSe-3)(54 and 25).With the high charge transfer and porous structure,CoNiSe/NC-3 shows good performance for both HER and OER.When current density reaches 10 m A cm-2,only 100 and 270 mV overpotentials are required for HER and OER,respectively.With the potential of 1.65 V,full water splitting also can be catalyzed by Co Ni Se/NC-3 with current density of 20 m A cm-2,suggesting that CoNiSe/NC-3 could be used as replacement for noble metal electrocatalysts.