Kinetic-Thermodynamic Promotion Engineering toward High-Density Hierarchical and Zn-Doping Activity-Enhancing ZnNiO@CF for High-Capacity Desalination

Despite the promising potential of transition metal oxides(TMOs)as capacitive deionization(CDI)electrodes,the actual capacity of TMOs electrodes for sodium storage is significantly lower than the theoretical capacity,posing a major obstacle.Herein,we prepared the kinetically favorable Zn_(x)Ni_(1−x)O electrode in situ growth on carbon felt(Zn_(x)Ni_(1−x)O@CF)through constraining the rate of OH^(−)generation in the hydrothermal method.Zn_(x)Ni_(1−x)O@CF exhibited a high-density hierarchical nanosheet structure with three-dimensional open pores,benefitting the ion transport/electron transfer.And tuning the moderate amount of redox-inert Zn-doping can enhance surface electroactive sites,actual activity of redox-active Ni species,and lower adsorption energy,promoting the adsorption kinetic and thermodynamic of the Zn_(0.2)Ni_(0.8)O@CF.Benefitting from the kinetic-thermodynamic facilitation mechanism,Zn_(0.2)Ni_(0.8)O@CF achieved ultrahigh desalination capacity(128.9 mgNaCl g^(-1)),ultra-low energy consumption(0.164 kW h kgNaCl^(-1)),high salt removal rate(1.21 mgNaCl g^(-1) min^(-1)),and good cyclability.The thermodynamic facilitation and Na^(+)intercalation mechanism of Zn_(0.2)Ni_(0.8)O@CF are identified by the density functional theory calculations and electrochemical quartz crystal microbalance with dissipation monitoring,respectively.This research provides new insights into controlling electrochemically favorable morphology and demonstrates that Zn-doping,which is redox-inert,is essential for enhancing the electrochemical performance of CDI electrodes.

Alkali metal cation effects on electrocatalytic CO_(2)reduction with iron porphyrins

The electrocatalytic CO_(2)reduction reaction(CO_(2)RR)has attracted increasing attention in recentyears.Practical electrocatalysis of CO_(2)RR must be carried out in aqueous solutions containing electrolytesof alkali metal cations such as sodium and potassium.Although considerable efforts havebeen made to design efficient electrocatalysts for CO_(2)RR and to investigate the structure–activityrelationships using molecular model complexes,only a few studies have been investigated the effectof alkali metal cations on electrocatalytic CO_(2)RR.In this study,we report the effect of alkali metalcations(Na^(+)and K^(+))on electrocatalytic CO_(2)RR with Fe porphyrins.By running CO_(2)RR electrocatalysisin dimethylformamide(DMF),we found that the addition of Na^(+)or K^(+)considerably improves thecatalytic activity of Fe chloride tetrakis(3,4,5‐trimethoxyphenyl)porphyrin(FeP).Based on thisresult,we synthesized an Fe porphyrin^(N)18C6‐FeP bearing a tethered 1‐aza‐18‐crown‐6‐ether(^(N)18C6)group at the second coordination sphere of the Fe site.We showed that with the tethered^(N)18C6 to bind Na^(+)or K^(+),^(N)18C6‐FeP is more active than FeP for electrocatalytic CO_(2)RR.This workdemonstrates the positive effect of alkali metal cations to improve CO_(2)RR electrocatalysis,which isvaluable for the rational design of new efficient catalysts.

Iron porphyrin with appended guanidyl group for significantly improved electrocatalytic carbon dioxide reduction activity and selectivity in aqueous solutions

Iron porphyrins have high activity and selectivity for electrocatalytic CO_(2)reduction reaction(CO_(2)RR)in nonaqueous solutions,but they usually display poor or moderate selectivity for CO_(2)RR in aqueous solutions because of the competitive hydrogen evolution reaction.Using water as the electrocatalytic reaction solvent is more favored because not only it is cheap,green and abundant but also it can sufficiently provide protons required for CO_(2)RR.Therefore,developing Fe porphyrins as electrocatalysts for efficient and selective CO_(2)RR in aqueous solutions is of both fundamental and practical significance.Herein,we report the design and synthesis of Fe porphyrin 1 with an appended guanidyl group and its electrocatalytic features for CO_(2)RR in both nonaqueous and aqueous solutions.In acetonitrile,Fe porphyrin 1 and its guanidyl-free analogue,tetrakis(3,4,5-trimethoxyphenyl)porphyrin 2,are both efficient for electrocatalytic CO_(2)-to-CO conversion,but the turnover frequency with 1(3.9´10^(5)s^(-1))is one order of magnitude larger than that with 2(1.7´10^(4)s^(-1)),showing the critical role of the appended guanidyl group in improving electrocatalytic CO_(2)RR activity.More importantly,in 0.1 mol L^(-1)KHCO_(3)aqueous solutions,1 showed very high selectivity for electrocatalytic CO_(2)-to-CO conversion with a Faradaic efficiency of 96%,while 2 displayed a Faradaic efficiency of 65%for the CO_(2)-to-CO conversion.This work is of significance to show the effect of appended guanidyl group on improving both activity and selectivity of Fe porphyrins for CO_(2)RR electrocatalysis.

Study on Extraction and Antioxidant Activity of Flavonoids from Dendranthema indicum

[Objectives] To determine the optimal extraction technology of flavonoids in Dendranthema indicum,and analyze the antioxidant activity of total flavonoids in D. indicum. [Methods]D. indicum was used as raw material to extract the total flavonoids by water extraction,alcohol extraction,freeze-thaw,microwave assisted extraction and ultrasonic extraction. [Results]Microwave assisted extraction had the highest extraction rate. Therefore,the microwave assisted extraction was selected as the main method,the ethanol aqueous solution was used as the solvent,and the single factor experiment was carried out with microwave power,ethanol volume fraction,solid-to-liquid ratio and microwave time as the variables. The optimal extraction process of flavonoids was microwave power 400 W,solid-to-liquid ratio 1 ∶ 30,extraction time60 s,ethanol volume fraction 70%,under this condition,the extraction yield was 10. 65 mg/g. The antioxidant activity of flavonoids in D. indicum was determined. The results showed that the highest scavenging rate of DPPH·free radicals was 47. 89%,and the highest scavenging rate of hydroxyl radicals was 98. 00%. [Conclusions]The flavonoids in D. indicum have excellent antioxidant activity. This study is expected to provide a basis for further development of D. indicum products.

An efficient approach for the treatment of radioactive waste perfluoropolyether lubricants via a synergistic effect of thermal catalysis and immobilization

Perfluoropolyether(PFPE)lubricants are a kind of high-molecular polymer with many excellent properties.However,the use of PFPEs in the nuclear industry can lead to partial decomposition and carrying radionuclides,resulting in a large amount of radioactive waste PFPE lubricants annually.Moreover,radioactive waste PFPE lubricants are difficult to be effectively treated due to their high stability,the risk of possible leakage of radionuclides,and hypertoxic fluorine-containing by-products.In this study,without any precedent,a strategy of Mn O_(2)-catalyzed decomposition and Na_(2)CO_(3)-immobilized conversion was proposed for PFPE lubricant decomposition and fluorine immobilization simultaneously based on the Lewis acid-base and oxygen vacancies concept.A high fluorine conversion efficiency of 95.4%was achieved.Meanwhile,the mechanism of decomposition suggested that Mn O_(2)mainly provided Lewis acid sites and attacked the(basic)fluorine or oxygen atoms in PFPE molecules.The decomposition of PFPE chains was proceed down and volatile fluorine-containing gas was released by partial electron transfer,intramolecular disproportionation reaction,and unzipping fashion.Subsequently,gas by-products could be further oxidized and then immobilized into fluoride salts by carbonate solid absorbents.Overall,this study provides a simple,safe,and potentially practical strategy for the harmless conversion of refractory fluorinated organic wastes,especially perfluoropolymers.

Effects of scenario-based carbon pricing policies on China's dual climate change mitigation goals: Does policy design matter?

Although the carbon pricing policy is a critical driving factor that will help China achieve economic growth,energy transition,and dual climate change mitigation goals,the kind of carbon pricing policy that will complement the country's current development situation remains controversial.We apply the World Induced Technical Change Hybrid(WITCH)model to explore the heterogeneity and synergy of different carbon pricing policies,and the results indicate that it will be challenging to achieve carbon neutrality before 2060.The study find that the combined policy-a mix of carbon tax and carbon market policies--has the optimal emission reduction effect but comes with the highest economic cost,proving to be unsuitable in the long run.The carbon tax policy is an important transitional means to assist in emission reduction,which can serve as an important supplement to carbon market policy and be phased out after the market mechanism matures.

Electropolymerization of cobalt porphyrins and corroles for the oxygen evolution reaction

Developing large-scale electrocatalysts using molecular complexes for the oxygen evolution reaction(OER)is of great importance. Herein, four cobalt porphyrins and corroles are deposited on electrode substrates using a simple and fast electropolymerization method. Our results showed that Co-1-P@CC, formed by electropolymerizing Co tetrakis(p-N-pyrrolylphenyl)porphyrin(Co-1-P) on carbon cloth(CC), is the most active OER catalyst in the examined Co porphyrins and corroles in alkaline aqueous solutions by displaying an onset overpotential of 380 m V. Long-term electrolysis tests confirmed the stability of these electropolymerized films by functioning as OER electrocatalysts.

Effects of water quality on the coagulation performances of humic acids irradiated with UV light

The presence of humic acid in drinking water treatment has received significant attention in recent years because of its adverse effects on the removal of many pollutants in coagulation. In this paper, the effects of water quality including pH, turbidity, alkalinity, and hardness on the removal of humic acid were investigated in a UV light hybridized coagulation process. Our results suggested that UV light radiation could effectively improve the removal rate of humic acid in coagulation under both neutral and basic conditions, and the variations of the selected water quality parameters had little adverse effect on the function of UV light. After UV light radiation, the removal rate of the nitro-humic acid （NHA） increased from 20% to 60% in coagulation, and increased further to 75% and 85% for the raw waters with 10.0 NTU kaolin and 100mg.L-1 hardness, respectively. In addition to NHA, the removal rates of the humic acid extracted from peat coal （PHA） and the humic acid provided by Japan metals and chemicals company （JHA） in coagulation were also improved, both in the range of 80%-90% after undergoing UV light radiation. By changing the radiation location from prior to coagulation to the flocculation process, similar experimental results were obtained. The formation of positive charged sites after UV light radiation was considered to be the primary factor that led to an enhanced removal of the humic acid in coagulation.

Preparation of Ce-TiO_2/carbon aerogel electrode and its performance in degradation of 4-chlorophenol

Ce-TiO2/CA（carbon aerogel） electrode was prepared by sol impregnation approach. The XRD（X-ray diffraction） and Raman spectra reveal that the TiO2 is anatase. The UV-vis diffuse reflectance spectra show that the optical absorption edge for Ce-TiO_2/CA is red-shifted to 535 nm compared with TiO_2/CA. Under visible light irradiation, the photocurrent density increment on Ce-TiO_2/CA is 75 times that on Ce-TiO_2/FTO（fluorine-doped tin oxide）. The electrochemical impedance spectroscopy reveals that the conductivity of CeTiO_2/CA is much better than the Ce-TiO_2/FTO. Furthermore, the Ce-TiO_2/CA can be used to the highest electrosorptive photodegradation for 4-chlorophenol wastewater degradation, which is ascribed predominantly to the efficient reduction of electron-hole pair recombination in the photocatalysts.

Tuning Electronic Structures of Covalent Co Porphyrin Polymers for Electrocatalytic CO_(2) Reduction in Aqueous Solutions

Improving the selectivity of the electrocatalytic CO_(2) reduction reaction(CO_(2)RR)over hydrogen evolution in aqueous solutions is required but challenging because the two reactions occur at close thermodynamic potentials and compete with each other.Herein,we report on the selective CO_(2)RR in aqueous solutions utilizing covalent Co porphyrin polymers with fine-tuned electronic structures.

Bioinspired iron porphyrins with appended poly-pyridine/amine units for boosted electrocatalytic CO_(2) reduction reaction

Developing highly efficient electrocatalysts for the CO_(2) reduction reaction(CO_(2)RR)has attracted increasing interest in the past decade.Herein,we report on the design and synthesis of Fe porphyrin 1 with an appended N,N-di(2-picolyl)ethylenediamine(DPEN)unit that boosts electrocatalytic activity for CO_(2)-to-CO conversion in acetonitrile with water as the proton source.By mimicking carbon monoxide dehydrogenase(CODH),1 has poly-pyridine/amine units located at the active site to form hydrogen-bonded water-containing networks that enable fast proton transfer.The protonated and positively charged DPEN unit can also stabilize CO_(2) reduction intermediates through electrostatic and hydrogen-bonding interactions.These factors make 1 a highly active electrocatalyst for the CO_(2)RR by achieving a TOFmax of 5.0​×​10^(4)​s^(−1) with water providing the protons.These critical roles of the DPEN unit in the CO_(2)RR are further supported by theoretical studies.This work is significant to highlight the benefits of using molecular catalysts to elucidate structural effects.

Long-term mercury variations in tree rings of the permafrost forest,northeastern China

Permafrost is a potential mercury(Hg)pool released by thawing,which can raise the risk of Hg pollution under global warming.Tree rings are useful archives of environment-specific Hg exposure over long periods.We determined Hg concentrations in tree rings of two dominant tree species(Larix gmelinii Rupr.and Pinus sylvestris var.mongolica)at permafrost sites in northeastern China.The biweighted mean Hg concentrations ranged from 0.36 to 3.96 ng g^(-1) from 1840 to 2014.The tree-ring width had no significant influence on the Hg concentration.Larch Hg increased slightly before the 1970 s and peaked in the 1990 s.However,the pine Hg concentration increased continuously until the 1930 s,decreased rapidly until the 1970 s,then rose to a peak in the late 1980 s.The change of Hg concentrations in larch and pine revealed a time offset of 4 to 5 years,which implied possibly high mobility of Hg in pine tree rings.Higher Hg concentrations from 1920 to 1960 and subsequent decreases in isolated permafrost forests revealed the local geographical Hg cycling history.Lower Hg concentrations and faster increases in larch suggest the role of additional winter Hg loading for the evergreen pine and species-specific differences in root absorption in response to melting permafrost.Our results highlight possible geographical impacts on tree-ring Hg records,improve understanding of Hg cycles in permafrost forest,and suggest a need to sample additional species in a range of permafrost environments.

Quantitative Analysis and Prediction of China's Natural Gas Consumption in Different Sectors Based on Bayesian Network

In view of the heterogeneity of natural gas consumption in different sectors in China,this paper utilizes Bayesian network(BN)to study the driving factors of natural gas consumption in power generation,chemical and industrial fuel sectors.Combined with Bayesian model averaging(BMA)and scenario analysis,the gas consumption of the three sectors is predicted.The results show that the expansion of urbanization will promote the gas consumption of power generation.The optimization of industrial structure and the increase of industrial gas consumption will enhance the gas consumption of chemical sector.The decrease of energy intensity and the increase of gas consumption for power generation will promote the gas consumption of industrial fuel.Moreover,the direct influencing factors of gas price are urbanization,energy structure and energy intensity.The direct influencing factors of environmental governance intensity are gas price,urbanization,industrial structure,energy intensity and energy structure.In 2025,under the high development scenario,China’s gas consumption for power generation,chemical and industrial fuel sectors will be 66.034,36.552 and 109.414 billion cubic meters respectively.From 2021 to 2025,the average annual growth rates of gas consumption of the three sectors will be 4.82%,2.18%and 4.43%respectively.