Modulation of IrO6 Chemical Environment for Highly Efficient Oxygen Evolution in Acid.

The sluggish kinetics of the oxygen evolution reaction (OER) limits the commercialization of oxygen electrochemistry, which plays a key role in renewable energy technologies such as fuel cells and electrolyzers. Herein, a facile and practical strategy is developed to successfully incorporate Ir single atoms into the lattice of transition metal oxides (TMOs). The chemical environment of Ir and its neighboring lattice oxygen is modulated, and the lattice oxygen provides lone-pair electrons and charge balance to stabilize Ir single atoms, resulting in the enhancement of both OER activity and durability. In particular, Ir0.08 Co2.92 O4 NWs exhibit an excellent mass activity of 1343.1 A g-1 and turnover frequency (TOF) of 0.04 s-1 at overpotentials of 300 mV. And this catalyst also displays significant stability in acid at 10 mA cm-2 over 100 h. Overall water splitting using Pt/C as the hydrogen evolution reaction catalyst and Ir0.08 Co2.92 O4 NWs as the OER catalyst takes only a cell voltage of 1.494 V to achieve 10 mA cm-2 with a perfect stability. This work demonstrates a simple approach to produce highly active and acid-stable transition metal oxides electrocatalysts with trace Ir.

Carbon Dots as Environment-Friendly and Efficient Corrosion Inhibitors for Q235 Steel in 1 M HCl.

To reduce the corrosion of Q235 steel, environment-friendly and efficient N-doped carbon dots (N-CDs) were synthesized using 4-amino salicylic acid (4-ASA) and l-histidine (l-His) as precursors. The corrosion inhibition behavior of N-CDs for Q235 steel in 1 M HCl solution was systematically investigated using a weight-loss experiment, an electrochemical test, and corrosion morphology. Results showed that N-CDs could effectively inhibit the corrosion of Q235 steel, and the inhibitory efficiency reached 93% at 50 mg L-1. Quantum chemistry and molecular dynamics were used to study the inhibition mechanism of N-CDs. The results demonstrated that N-CDs exhibited a strong adsorption force on metal and the adsorption process followed the Langmuir adsorption isotherm, indicating physical/chemical mixed adsorption.

On-site electrochemical determination of phosphate with high sensitivity and anti-interference ability in turbid coastal waters.

Phosphate is considered to be an important biogenic element and responsible for eutrophication in aquatic ecosystems, existing in both dissolved and absorbed forms. Due to the complex matrix of coastal seawater, a high sensitivity and anti-interference method for phosphate detection is required for environmental protection. In this study, a novel electrochemical method was proposed based on reduced graphene oxide-ordered mesoporous carbon screen-printed electrode (rGO-OMC/SPE) analysis, allowing sensitivity and reliable determination of phosphate in turbid coastal waters. Combining the good absorption capacity of OMC with the excellent electroconductivity of rGO, the fabricated electrode exhibits improved signal responses, enhanced by up to 43-fold. The platform was evaluated using turbidity interference test with good recovery percentages comprised between 96% and 105% in different phosphate concentration, and salinity interference test between 92% and 105%, respectively. A linear range from 0.2 to 150 µM phosphate was achieved, with a detection limit of 0.05 µM (s/n = 3). The fabricated platform was successfully used for on-site analysis of phosphate in turbid coastal waters. This reliable and effective method for the analysis of phosphate in turbid coastal waters allows for sensitivity and anti-interference determination, while also representing a significant step towards comprehensive and convenient analysis of phosphorus species.

Nanocomposite based on graphene and intercalated covalent organic frameworks with hydrosulphonyl groups for electrochemical determination of heavy metal ions.

An electrochemical sensor constructed by intercalated composites was developed for determination of heavy metal ions. The intercalated composites were composed of hydrosulphonyl functional covalent organic frameworks (COF-SH) and graphene (G). The presence of numerous adsorption sites, such as 18 sulfur atoms and 30 nitrogen atoms per big circle of COFs on COF-SH, was beneficial for the accumulation of heavy metals, while the graphene enhanced the electrical conductivity. The obtained sensor under the optimal conditions successfully detected the presence of heavy metal ions in coastal water samples at concentrations ranging from 1 to 1000 µg L-1. The detection limits of Cd (II), Pb (II), Cu (II), and Hg (II) were 0.3, 0.2, 0.2, and 1.1 µg L-1, respectively. Furthermore, the sensor still exhibited good stability after multiple uses less than 5%. When it is used in the analysis of actual samples, the recovery of standard addition is higher than 95%. In sum, the combination of hydrosulphonyl functional COFs with graphene looks very promising for the assembly of sensors with high sensitivity toward the determination of heavy metal ions for coastal environmental monitoring.

Quantitative assessment on soil concentration of heavy metal-contaminated soil with various sample pretreatment techniques and detection methods.

Detection and quantification of heavy metals in soil samples are significant in terms of environmental monitoring and risk assessment for metals. In order to improve the accuracy and precision to detect heavy metal, in this study, four standard samples (NASS-4, NASS-5, NASS-9, and NASS-16) were analyzed by evolving heating (electric heating plate, water bath, and microwave) and acidic systems (includes HCl, HNO3, HF, and HClO4). The result shows that different pretreatment methods have different effects on the extraction of heavy metal elements and five heavy metal elements (Cu, Zn, Pb, Ni, and Cr) were selected for optimization through pretreatment methods. Although the contents of heavy metals were same but we found diversity in the results. Under optimal conditions, the selected standard samples were analyzed by inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma atomic emission spectroscopy (ICP-AES), and atomic absorption spectroscopy (AAS), and the results were compared. The results show that different elements have their own most suitable detection methods, such as for Pb, the most suitable method is ICP-MS; and for Zn, the most suitable method is AAS. Pretreatment methods and detection techniques are combined to find and improve accuracy of results for certain elements. This study provides a reliable detection method for the accurate detection of heavy metals in the environment.

[Determination of Bi in Soils and Sediments by Atomic Fluorescence Spectrometry].

A method for determination of the contents of Bi in soils and sediments by atomic fluorescence spectrophotometry (AFS) was established by using aqua regia as the dissolved medium. In this paper, the instrument parameters, load flow and reducing agent concentration were optimized. Compared with microwave digestion and electric heating plate digestion, water bath digestion demonstrated the better digestion efficiency and was most commonly used. Under the optimal experimental conditions, the detection limit (LOD) was 0.01 mg·kg-1 (sample quantity 0.500 0 g, sample volume 50 mL), and the limit of quantitation (LOQ) was 0.04 mg·kg-1. The results were in good agreement with the centified value, and the relative error was -4.7%~-2.0%. For determination of soil and sediment actual samples, the relative standard deviation (RSD) were 2.5%~3.4% and 3.1%~3.4%, respectively, and the recoveries of the method respectively ranged from 97.6%~102% and 99.5%~104%.

Determination of Beryllium in Soil and Sediment by Graphite Furnace Atomic Absorption with a Microwave-Acid Digestion Method.

A method for determination of beryllium in soils and sediments by microwave-acid digestion/graphite furnace atomic absorption (GFAA) is described. In this paper, the working conditions of the instrument are optimized, the drawing of calibration curve is expounded, the pretreatment process of soil and sediments (including microwave heating process and the selection of digestion system) is discussed, and the interference of coexisting elements is examined. The sample was pretreated by microwave digestion parameters using HNO3/ HCl/HF mixed acid system. The method is fast and simple without matrix modifier, and has no interference by coexisting ions, and has high repeatability and reproducibility. Under the optimal experimental conditions, the limit of detection (LOD) is 0.004 9 mg · kg⁻¹ (sample quantity 0.200 0 g, sample volume 25 mL), and the limits of quantitation (LOQ) is 0.20 mg · kg⁻¹. This method is used to measure the standard samples and actual samples, whether in the laboratory, or between laboratories, has good accuracy and precision.

Donor-acceptor moiety functionalized covalent organic frameworks for boosting charge separation and H2 photogeneration.

Covalent organic frameworks (COFs) have a broad prospect to be used as a photocatalytic platform to convert solar energy into valuable chemicals due to their tunable structures and rich active catalytic sites. However, constructing COFs with tuned sp2-carbon donor-acceptor moiety remains an enormous challenge. Herein, we synthesized two new fully π-conjugated cyano-ethylene-linked COFs containing benzotrithiophene as functional group by Knoevenagel polycondensation reaction. The accetpor 2,2'-bipyridine unit in BTT-BpyDAN-COF skeleton favored the formation of a intermolecular specific electron transport pathway with the donor benzotrithiophene, and thereby promoted charge separation and transfer efficiency. Specifically, a donor-acceptor (D-A) type BTT-BpyDAN-COF exhibited high hydrogen evolution rate of 10.1 mmol g-1h-1 and an excellent apparent quantum efficiency of 4.83 % under visible light irradiation.

Recent advances on covalent organic frameworks (COFs) as photocatalysts: different strategies for enhancing hydrogen generation.

The excessive use of traditional fossil fuels has led to energy and environmental pollution problems. Solar-driven hydrogen generation has attracted much attention in recent years owing to its environmental friendliness and economic feasibility. So far, a series of photocatalysts have been advanced. Unfortunately, these photocatalysts face some issues including poor sunlight harvesting ability, weak photo-corrosion resistance, broad band gap, bad stability, inferior hydrogen evolution rate and so on. It just so happens that COFs have emerged to provide an opportunity for settling these issues. Covalent organic frameworks (COFs), a novel family of porous materials with regular porosity and tunable physicochemical structures, have been extensively explored as photocatalysts for hydrogen production. Moreover, their photocatalytic activities are highly structurally dependent. In this review, we mainly focus on the linkage chemistry and disparate strategies for boosting COF-based photocatalytic hydrogen generation performance in detail. The prospects and obstacles confronted in the development of COF-based photocatalysts and proposals to settle dilemmas are also discussed.

A novel graphene oxide-dicationic ionic liquid composite for Cr(VI) adsorption from aqueous solutions.

A novel graphene oxide-dicationic ionic liquid composite (GO-DIL) was prepared by modifying graphene oxide (GO) with a dicationic ionic liquid (DIL), 3,3'-(butane-1,4-diyl) bis (1-methyl-1H-imidazol-3-ium) chloride ([C4(MIM)2]Cl2). GO and GO-DIL were characterized by SEM, BET, FTIR, and XPS, and the materials were used for Cr(VI) adsorption. Batch adsorption studies showed that adsorption reached equilibrium within 40 min, and the optimal pH was 3, where the electrostatic attraction between GO-DIL and Cr(VI) was maximized. The maximum theoretical Cr(VI) adsorption capacity (qm) was 271.08 mg g-1, and qm remained above 228.00 mg g-1 after five cycles. The adsorption data were fitted well by both the pseudo-first-order kinetic model and the Langmuir model. Furthermore, thermodynamics calculations revealed that adsorption was a spontaneous endothermic process. Importantly, electrostatic attraction between Cr(VI) and the protonated imidazole N+ of GO-DIL played a critical role in Cr(VI) adsorption, and Cr(VI) was reduced to Cr(III). Thus, GO-DIL is predicted to be an effective adsorbent for Cr(VI) and other heavy metal ions in wastewater.

Evaluating the metabolic functional profiles of the microbial community and alfalfa (Medicago sativa) traits affected by the presence of carbon nanotubes and antimony in drained and waterlogged sediments.

Antimony (Sb) is the ubiquitous re-emerging contaminant greatly accumulated in sediments which has been revealed risky to ecological environment. However, the impacts of Sb (III/V) on microbes and plants in sediments, under different water management with presence of engineering materials are poorly understood. This study conducted sequential incubation of sediments (flooding, draining and planting) with presence of multiwall carbon nanotubes (MWCNTs) and Sb to explore the influence on microbial functional diversity, Sb accumulation and alfalfa traits. Results showed that water management and planting led to greater impacts of sediment enzyme activities and microbial community metabolic function and bioavailable Sb fractions (defined as sum of acid-soluble fraction and reducible fraction, F1 + F2). Available fractions of Sb (V) showed higher correlation to microbial metabolism (r = 0.933) than that of Sb (III) (r = -0.480) in planting stage. MWCNTs with increasing concentrations (0.011%, w/w) positively correlated to microbial community metabolic function in planting stage whereas resulted in decreasing of Sb (III/V) concentrations in alfalfa, although 0.01% MWCNT led to increase of Sb (V) and decrease of Sb (V) by 50.97% and 32.68% respectively. This study provided information for investigating combined ecological impacts of heavy metal and engineering materials under different water managing sediments.

Simple descriptor derived from symbolic regression accelerating the discovery of new perovskite catalysts.

Symbolic regression (SR) is an approach of interpretable machine learning for building mathematical formulas that best fit certain datasets. In this work, SR is used to guide the design of new oxide perovskite catalysts with improved oxygen evolution reaction (OER) activities. A simple descriptor, µ/t, where µ and t are the octahedral and tolerance factors, respectively, is identified, which accelerates the discovery of a series of new oxide perovskite catalysts with improved OER activity. We successfully synthesise five new oxide perovskites and characterise their OER activities. Remarkably, four of them, Cs0.4La0.6Mn0.25Co0.75O3, Cs0.3La0.7NiO3, SrNi0.75Co0.25O3, and Sr0.25Ba0.75NiO3, are among the oxide perovskite catalysts with the highest intrinsic activities. Our results demonstrate the potential of SR for accelerating the data-driven design and discovery of new materials with improved properties.

The Electrochemical Oxidation of Hydroquinone and Catechol through a Novel Poly-geminal Dicationic Ionic Liquid (PGDIL)-TiO2 Composite Film Electrode.

A novel poly-geminal dicationic ionic liquid (PGDIL)-TiO2/Au composite film electrode was successfully prepared by electrochemical polymerization of 1,4-bis(3-(m-aminobenzyl)imidazol-1-yl)butane bis(hexafluorinephosphate) containing polymerizable anilino groups in the electrolyte containing nano-TiO2. The basic properties of PGDIL-TiO2/Au composite films were studied by SEM, cyclic voltammetry, electrochemical impedance spectroscopy, and differential pulse voltammetry. The SEM results revealed that the PGDIL-TiO2 powder has a more uniform and smaller particle size than the PGDIL. The cyclic voltammetry results showed that the catalytic effect on electrochemical oxidation of hydroquinone and catechol of the PGDIL-TiO2 electrode is the best, yet the Rct of PGDIL-TiO2 electrode is higher than that of PGDIL and TiO2 electrode, which is caused by the synergistic effect between TiO2 and PGDIL. The PGDIL-TiO2/Au composite electrode presents a good enhancement effect on the reversible electrochemical oxidation of hydroquinone and catechol, and differential pulse voltammetry tests of the hydroquinone and catechol in a certain concentration range revealed that the PGDIL-TiO2/Au electrode enables a high sensitivity to the differentiation and detection of hydroquinone and catechol. Furthermore, the electrochemical catalytic mechanism of the PGDIL-TiO2/Au electrode was studied. It was found that the recombination of TiO2 improved the reversibility and activity of the PGDIL-TiO2/Au electrode for the electrocatalytic reaction of HQ and CC. The PGDIL-TiO2/Au electrode is also expected to be used for catalytic oxidation and detection of other organic pollutants containing -OH groups.

Adsorption of Ni2+ and Pb2+ from water using diethylenetriamine-grafted Spirodela polyrhiza: behavior and mechanism studies.

Novel adsorbent, diethylenetriamine-grafted Spirodela polyrhiza (DSP), was synthesized via modifying natural S. polyrhiza (SP) with diethylenetriamine by cross-linking with epichlorohydrin and applied to adsorb Ni2+ and Pb2+ from water. The effecting parameters on adsorption of Ni2+ and Pb2+ such as adsorbent dosage, pH, contact time, temperature, and initial concentration were studied through equilibrium experiments. The adsorption of Ni2+ and Pb2+ followed the pseudo-second-order model and the Langmuir isotherm adsorption model. The study discusses thermodynamic parameters, including changes in Gibbs free energy, entropy, and enthalpy, for the adsorption of Ni2+ and Pb2+ on DSP, and revealed that the adsorption process was spontaneous and exothermic under natural conditions. The maximum Ni2+ and Pb2+ adsorption capacities of DSP were 33.02 and 36.50 mg/g, respectively. The newly prepared materials were characterized through scanning electron microscopy (SEM), mapping analysis, and zeta potential analysis. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analyses indicated that functional groups (-OH and N-H) were involved in Ni2+ and Pb2+ adsorption. Notably, DSP can be easily regenerated and reused for multiple cycles. Therefore, DSP is a promising adsorbent for effective Ni2+ and Pb2+ removal.

Speciation determination of iron and its spatial and seasonal distribution in coastal river.

In this study, the speciation of iron (Fe), including total Fe (TFe) and acidified dissolved Fe (ADFe), was assessed by fast cathodic absorption stripping voltammetry, using a gold electrode and 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) as a novel complexing agent for Fe. The validity and accuracy of this method were compared with the standard spectrophotometry and tested by the standard samples. Under optimized conditions, the Fe response was linear within the range of 0.01 to 1 µM with a detection limit of 1.2 nM. To further validate this method, the variation in concentrations of TFe and ADFe were investigated at twelve sampling stations in a local coastal river, in both the dry and wet season. Additionally, to further understand the interaction between Fe and environmental factors, the relationships between the concentration of Fe species and dissolved oxygen (DO) and salinity were also discussed.

Detection of Cu2+ in Water Based on Histidine-Gold Labeled Multiwalled Carbon Nanotube Electrochemical Sensor.

Based on the strong interaction between histidine and copper ions and the signal enhancement effect of gold-labeling carbon nanotubes, an electrochemical sensor is established and used to measure copper ions in river water. In this study the results show that the concentrations of copper ion have well linear relationship with the peak current in the range of 10-11-10-7 mol/L, and the limit of detection is 10-12 mol/L. When using this method to detect copper ions in the Xiangjiang River, the test results are consistent with the atomic absorption method. This study shows that the sensor is convenient to be used in daily monitoring of copper ions in river water.