Effect of chloride ions on the corrosion behavior of carbon steel in an iron bacteria system

Reclaimed water used as circulating cooling water can effectively relieve water stress, but the corrosion problem in it is very prominent. In particular, Cl⁻ and iron bacteria (IB) are important influencing factors of corrosion behavior in a circulating water environment, and both of them often coexist in circulating water systems, so it is crucial to study their synergistic effects. This paper investigated the effect of Cl⁻ on the corrosion behavior of carbon steel in the IB system by use of weight loss measurements, electro-chemistry and X-ray photoelectron spectroscopy (XPS). In the first 1–9 days of the experiment, the increase of Cl⁻ concentration led to an increase of corrosion rate and a decrease of anode potential and charge transfer resistance at the interface. The corrosion rate of the 4Cl_IB condition reached 0.45 mm a⁻¹ in the 1st day, which was 1.47 and 1.15 times that of 3Cl_IB and 1Cl_IB, and its anode potential was 22.6% and 33.8% lower than that of 3Cl_IB and 1Cl_IB. This indicates that a higher concentration of Cl⁻ made the anodic reaction easier and the corrosion more severe. However, after 9 days, a decline in the corrosion rate was recorded at similarly high Cl⁻ concentrations. On the 15th day, the corrosion rates for 3Cl_IB and 4Cl_IB were 7.0% and 15.6% lower compared to the 1Cl_IB condition. At this stage, the anode potential and film resistance had increased significantly, to become the dominant factors controlling the corrosion reaction. On the 15th day, the β_a values of 1Cl_IB, 3Cl_IB and 4Cl_IB were 1.2, 1.5 and 1.7 times higher than those of the 1st day, and the highest R_b value of 1592.1 Ω cm² was obtained for the 4Cl_IB condition, which was 1.9 times higher than that of R_ct. In the early stage of corrosion, the surface of the carbon steel was enriched in Cl⁻ due to their high concentration, and the Cl⁻ could easily destroy the developing corrosion product film and promote the generation of Fe²⁺. At the same early stage, the growth of IB was enhanced, and the metabolism of IB was promoting local corrosion. However, in the later stage of corrosion, biofilms had an increasing effect on corrosion. A high concentration of Cl⁻ accelerated biofilm growth and densified the corrosion product layer which subsequently hindered the anodic reaction and thus inhibited corrosion.

In the early stage, Cl⁻ destroys the corrosion product film and promotes localized corrosion. In the later stage, a high concentration of Cl⁻ accelerates biofilm growth and densifies the corrosion product layer, thereby inhibiting corrosion.     

Correlation between electrochemical properties and stress corrosion cracking of super 13Cr under an HTHP CO2 environment

The susceptibility of super 13Cr steel to stress corrosion cracking (SCC) was assessed through slow strain rate testing in simulated formation water saturated with CO₂ under a high-temperature and high-pressure (HTHP) environment. The evolution, morphology, and chemistry of fracture and corrosion products on the steel surface were evaluated using in situ electrochemical methods and surface analysis. Results indicate that the occurrence of pitting corrosion increases SCC susceptibility. At 150 °C, the degradation of a surface film induces pitting corrosion because of an increase in anodic processes. The presence of Cl⁻ causes film porosity, and CO₂ reduces the Cr(OH)₃/FeCO₃ ratio in the inner film, which further promotes Cl⁻-induced porosity.

The degradation of a surface film induces pitting corrosion, which further increases SCC susceptibility.     

Influence of Cl− ions on anodic polarization behaviour of API X80 steel in high potential/current density conditions in Na2SO4 solution

Pipeline steel has considerable risk of corrosion in the high voltage direct current interference cases. Thus, under high potential/current density conditions, the anodic polarization behaviour of X80 steel in Na₂SO₄ solution and the influence of Cl⁻ ions were investigated using reversed potentiodynamic polarization, the current interrupt method, galvanostatic polarization, scanning electron microscopy, and X-ray photoelectron spectroscopy. In the Na₂SO₄ solution free of Cl⁻ ions, steel was passivated above 0.120 A cm⁻² and the potential increased from −0.32 V to 1.43 V. The passive film was composed of Fe₃O₄, γ-Fe₂O₃, and FeOOH. The addition of Cl⁻ ions observably influenced the passivation by attacking the passivate film. Low concentration of Cl⁻ ions (<5 mg L⁻¹ NaCl) could set higher demands of current density to achieve passivation and increase the requirement of potential to maintain passivation. A high concentration of Cl⁻ ions (>5 mg L⁻¹ NaCl) completely prevented passivation, showing strong corrosiveness. Thus, the X80 steel was corroded even under high-current-density conditions. The corrosion products were mainly composed of Fe₃O₄, α-Fe₂O₃, and FeOOH.

X80 steel gets passivated in high potential/current density conditions in Na₂SO₄ solution. Low concentration of Cl⁻ ions weakens the passivation. High concentration of Cl⁻ ions totally prevents the passivation.     

Control of Fe3+ coordination by excess Cl− in alcohol solutions

We spectroscopically investigated coordination state of Fe³⁺ in methanol (MeOH) and ethanol (EtOH) solutions against Cl⁻ concentration ([Cl⁻]). In both the system, we observed characteristic absorption bands due to the FeCl₄ complex at high-[Cl⁻] region. In the MeOH system, the proportion (r) of [FeCl₄]⁻ exhibits a stationary value of 0.2–0.3 in the intermediate region of 10 mM < [Cl⁻] < 50 mM, which is interpretted in terms of [FeCl_nL_6−n]³⁻ⁿ (n = 1 and 2). In the EtOH system, r steeply increases from 0.1 at [Cl⁻] = 1.5 mM to 0.7 at [Cl⁻] = 3.5 mM, indicating direct transformation from [FeL₆]³⁺ to [FeCl₄]⁻. We further found that the coordination change significantly decreases the redox potential of Fe²⁺/Fe³⁺.

Fe³⁺ coordination in alcohol solution can be controlled by the Cl⁻ concentration ([Cl⁻]). The coordination state changes from FeL₆ (L: solvent molecule) to FeCl₄ type via FeCl_nL_6−n with increases in [Cl⁻].     

Roles of hydroxyl and carbonate radicals in bisphenol a degradation via a nanoscale zero-valent iron/percarbonate system: influencing factors and mechanisms

In this work, nanoscale-zero-valent iron (nZVI) was applied to activate sodium percarbonate (SPC) to eliminate bisphenol A (BPA), which poses a risk to ecological and human health as a typical endocrine disruptor. The influence of nZVI loading, SPC dosing, initial pH, and the presence of inorganic anions (including Cl⁻, HPO₄²⁻, NO₃⁻ and NO₂⁻) and humic acid on BPA removal by the nZVI/SPC system were investigated. Based on the scavenger test results, ˙OH and CO₃˙⁻ participated in the degradation of BPA, and ˙OH was illustrated to be the dominant radical. The X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analysis suggested that surface iron oxide generation, electron transfer and Fe²⁺ release were the main processes of the SPC activation by nZVI. Moreover, BPA transformation products were detected by LC-MS allowing the proposal of a possible degradation pathway of BPA. Along with the degradation of the parent compound BPA, the total organic carbon (TOC) gradually decreased, while the bio-toxicity increased at the initial stage of the reaction (0–3 min) and then decreased to a lower level rapidly at 20 min. Overall, this study evidenced the feasibility of the nZVI/SPC system to efficiently degrade BPA, broadening the applications of nZVI in wastewater treatment.

Both ˙OH and CO₃˙⁻ participated in the degradation of BPA in the nZVI/SPC system, and ˙OH was the main radical.     

Ca(OH)2-mediated activation of peroxymonosulfate for the degradation of bisphenol S

Alkaline substances could activate peroxymonosulfate (PMS) for the removal of organic pollutants, but relatively high alkali consumption is generally required, which can cause too high pH of the solution after the reaction and lead to secondary pollution. Within this study, PMS activated by a relatively low dosage of Ca(OH)₂ (1 mM) exhibited excellent efficiency in the removal of bisphenol S (BPS). The pH of the solution declined to almost neutral (pH = 8.2) during the reaction period and conformed to the direct emission standards (pH = 6–9). In a typical case, BPS was completely degraded within 240 min and followed the kinetics of pseudo-first-order. The degradation efficiency of BPS depended on the operating parameters, such as the Ca(OH)₂, PMS and BPS dosages, initial solution pH, reaction temperature, co-existing anions, humic acid (HA), and water matrices. Quenching experiments were performed to verify that singlet oxygen (¹O₂) and superoxide radicals (O₂˙⁻) were the predominant ROS. Degradation of BPS has been significantly accelerated as the temperature increased. Furthermore, degradation of BPS could be maintained at a high level across a broad range of pH values (5.3–11.15). The SO₄⁻, NO₃⁻ did not significantly impact the degradation of BPS, however, both HCO₃⁻ and HA inhibited oxidation of BPS by the Ca(OH)₂/PMS system, and Cl⁻ had a dual-edged sword effect on BPS degradation. In addition, based on the 4 identified intermediates, 3 pathways of BPS degradation were proposed. The degradation of BPS was lower in domestic wastewater compared to other naturals waters and ultrapure; nevertheless, up to 75.86%, 77.94% and 81.48% of BPS was degraded in domestic wastewater, Yaohu Lake water and Poyang Lake water, respectively. Finally, phenolic chemicals and antibiotics, including bisphenol A, norfloxacin, lomefloxacin hydrochloride, and sulfadiazine could also be efficiently removed via the Ca(OH)₂/PMS system.

Ca(OH)₂ can activate PMS to effectively remove BPS, and it can meet the requirements of direct discharge after reaction.     

Efficient one-pot green synthesis of tetrakis(acetonitrile)copper(i) complex in aqueous media

New simple, fast, effective and environmentally friendly one-pot method for the synthesis of extensively used tetrakis(acetonitrile)copper(i) complexes with BF₄⁻, PF₆⁻ and ClO₄⁻ counterions is invented and optimized. The approach suggested allows using water as solvent and minimizes amounts of toxic organic reagents in the synthetic protocol.

New simple, fast, effective and environmentally friendly one-pot method for the synthesis of extensively used tetrakis(acetonitrile)copper(i) complexes with BF₄⁻, PF₆⁻ and ClO₄⁻ counterions is invented and optimized.     

Structure-modulated CaFe-LDHs with superior simultaneous removal of deleterious anions and corrosion protection of steel rebar

The three anionic species; chloride (Cl⁻), sulfate (SO₄²⁻), and carbonate (CO₃²⁻), are typical chemical factors that environmentally accelerate failure of concrete structures with steel rebar through long-term exposure. Efficient removal of these deleterious anions at the early stage of penetration is crucial to enhance the lifespan and durability of concrete structures. Here, we synthesize CaFe-layered double hydroxide (CaFe-LDHs) by a simple one-step co-precipitation technique and structural modulation by calcination process. It is applied for the removal of Cl⁻, SO₄²⁻, and CO₃²⁻ anions as well as corrosion inhibition on steel rebar in aqueous solutions. The synthesized CaFe-LDHs with phase transfer show notable improvement of removal capacity (Q_max) toward Cl⁻ and SO₄²⁻ over 3.4 times and over 5.69 times, respectably, then those of previous literatures. Furthermore, the steel rebar exposed to an aqueous solution containing the three anionic sources shows a fast corrosion rate (1876.56 × 10⁻³ mm per year), which can be remarkably inhibited showing 98.83% of corrosion inhibition efficiency when it is surrounded by those CaFe-LDHs. The novel adsorption mechanisms of these CaFe-LDHs-induced crystals and corresponding corrosion protection properties are elucidated drawing on synergy of memory effects and chemical reactions.

The three anionic species; chloride (Cl⁻), sulfate (SO₄²⁻), and carbonate (CO₃²⁻), are typical chemical factors that environmentally accelerate failure of concrete structures with steel rebar through long-term exposure.     

First-principles study of coadsorption of Cu2+ and Cl− ions on the Cu (110) surface

Motivated by the importance of Cl⁻ in the industrial electrolytic Cu plating process, we study the coadsorption of Cl⁻ and Cu²⁺ on the Cu (110) surface using first-principles density functional theory (DFT) calculations. We treat the solvent implicitly by solving the linearized Poisson–Boltzmann equation and evaluate the electrochemical potential and energetics of ions with the computational hydrogen electrode approach. We find that Cl⁻ alone is hardly adsorbed at sufficiently negative electrochemical potentials μ_Cl but stable phases with half and full Cl⁻ coverage was observed as μ_Cl is made more positive. For Cl⁻ and Cu²⁺ coadsorption, we identified five stable phases for electrode biases between −2V < U_SHE < 2V, with two being Cl⁻ adsorption phases, two being Cl⁻ + Cu²⁺ coadsorption phases and one being a pure Cu²⁺ adsorption phase. In general, the free energy of adsorption for the most stable phases at larger |U_SHE| are dominated by the energy required to move electrons between the system and the Fermi level of the electrode, while that at smaller |U_SHE| are largely dictated by the binding strength between Cl⁻ and Cu²⁺ adsorbates on the Cu (110) substrate. In addition, by studying the free energy of adsorption of Cu²⁺ onto pristine and Cl⁻ covered Cu (110), we conclude that the introduction of Cl⁻ ion does not improve the energetics of Cu²⁺ adsorption onto Cu (110).

Free energy of adsorption for the most stable phases predicted by DFT calculations as a function of electrode potential.     

Deuterium equilibrium isotope effects in a supramolecular receptor for the hydrochalcogenide and halide anions

We highlight a convenient synthesis to selectively deuterate an aryl C–H hydrogen bond donor in an arylethynyl bisurea supramolecular anion receptor and use the Perrin method of competitive titrations to study the deuterium equilibrium isotope effects (DEIE) of anion binding for HS⁻, Cl⁻, and Br⁻. This work highlights the utility and also challenges in using this method to determine EIE with highly reactive and/or weakly binding anions.

We highlight a convenient synthesis to selectively deuterate an aryl C–H hydrogen bond donor in a supramolecular anion receptor and use competitive titrations to study the deuterium equilibrium isotope effects (DEIE) in binding HS⁻, Cl⁻, and Br⁻.

Molecular recognition and host–guest binding in both biological and synthetic systems are often driven by a mixture of competitive and additive primarily non-covalent interactions. Understanding the role of each of these forces in a host–guest system can reveal insights into the driving forces behind binding and help inform on the molecular design of future hosts.^1–3 Equilibrium isotope effects (EIE), also referred to as binding isotope effects (BIE) in structural molecular biology,⁴ measure the effect of isotopic substitution on supramolecular interactions through changes in the vibrational energy of the substituted bond. These studies can be used to elucidate the complex non-covalent forces involved in host conformational changes and host–guest binding.^5–8Examples from structural molecular biology have demonstrated that EIEs can reveal mechanistic information in enzyme–ligand binding events.^4,9 Isotopic substitution in synthetic supramolecular systems has been used both for labelling purposes and for studying individual non-covalent interactions. For example, Bergman, Raymond, and coworkers used deuterium equilibrium isotope effects (DEIE) to study benzylphosphonium cation guest binding in a self-assembled supramolecular complex in aqueous solution.¹⁰ From these DEIE studies, the authors found that attractive cation⋯π interactions in the interior of the host were important for promoting guest binding, and that C–H⋯π and π⋯π interactions were relatively small contributors. In another example, Shimizu and coworkers studied the DEIE on the strength of C–H⋯π interactions in their molecular balances.¹¹ Both computational and experimental results showed that the strength of C–H⋯π and C–D⋯π interactions were about equal, settling the debate on which interaction is stronger and easing concerns about using deuteration for spectroscopic and labelling applications.Previously, we used DEIE to study Cl⁻ binding with the arylethynyl bisurea anion receptor 1^H/D (Fig. 1) in DMSO-d₆.¹² We found an experimental DEIE of 1.019 ± 0.010, which matched the computationally-predicted DEIE of 1.020. Further computational analysis determined that the DEIE was due to a distorted N–H⋯Cl⁻ hydrogen bond geometry, which resulted in changes in the C–H/D bond vibrational energy in the host–guest complex. In addition, Paneth and coworkers performed a computational study with 1^H and other hydrogen bonding supramolecular Cl⁻ receptors to determine the EIE of ^35/37Cl⁻ binding in these hosts.¹³ Because isotope effects, both equilibrium and kinetic, originate solely from changes in the vibrational energy of the isotopically labelled bond, the EIE arising from this study came from changes in the vibrational energies of the bonds in the supramolecular hosts when participating in hydrogen bonding with Cl⁻ isotopes. Indeed, a linear relationship was observed between the hydrogen bond donor (D) D–H bond lengths in the host–guest complex and the computed ^35/37Cl EIE.Open in a separate windowFig. 1Arylethynyl bisurea receptors 1^H and 1^D used in our previous DEIE study of Cl⁻ binding. Related receptors 2^H and 2^D are used in this study to avoid reaction of the nitro group with HS⁻.Previous EIE studies with receptor 1^H/D have focused on Cl⁻ binding; however, to the best of our knowledge, no work has yet investigated the EIE of hydrosulfide (HS⁻) binding in this or other systems. HS⁻ is a highly reactive anion that plays crucial roles in biology. At physiological pH, HS⁻ is favored in solution by a 3 : 1 ratio over its conjugate acid, hydrogen sulfide (H₂S). H₂S has been identified as the third physiological gasotransmitter alongside CO and NO and plays essential roles in physiological systems.¹⁵ Despite its high nucleophilicity and redox activity, HS⁻ has been observed to be bound through non-covalent interactions in the protein crystal structure of a bacterial ion channel¹⁶ and in the turn-over state of vanadium-containing nitrogenase.¹⁷ The supramolecular chemistry of HS⁻ is under-studied in synthetic supramolecular receptors, likely due to the inherent high reactivity of HS⁻. Indeed, we are aware of only three families of receptors that have been shown to reversibly bind HS⁻.^18–21Recently, we used a series of arylethynyl bisurea anion receptors to investigate and demonstrate a linear free energy relationship between the polarity of a non-traditional C–H hydrogen bond donor and the solution binding energy of HS⁻, HSe⁻, Cl⁻ and Br⁻.¹⁴ A major and unexpected finding of this study was that HS⁻ demonstrated a significant increase in sensitivity towards the polarity of the C–H hydrogen donor over HSe⁻, Cl⁻ and Br⁻. Although increasing the polarity of the C–H hydrogen bond donor did not lead to changes in selectivity between Cl⁻, Br⁻, and HSe⁻, we observed a 9-fold increase in selectivity for HS⁻ over Cl⁻, suggesting a fresh approach to selective HS⁻ recognition using non-covalent interactions. In this current study, we label the C–H hydrogen bond donor in an arylethynyl bisurea receptor with a deuterium atom (2^H/D, Fig. 1) to further investigate this apparent preference of polar C–H H-bond donors for HS⁻ over Cl⁻ and Br⁻ through DEIE.Receptor 2^H is a previously reported anion receptor for HS⁻, Cl⁻, and Br⁻ and was prepared by established methods.¹⁴ Deuterium labelling of the isotopologue 2^D was achieved by selective monodeuteration of intermediates through methods similar to those reported in the literature (Scheme 1).²² The diazonium salt 3 was synthesized in a 71% yield from 2,6-diiodo-4-trifluoromethylaniline.²³ Dediazonation in DMF-d₇ is catalyzed by FeSO₄ and allows for selective synthesis of monodeuterated intermediate 4. The deuteration step proceeds through a radical pathway that uses DMF-d₇ as the deuterium source. This deuteration reaction provides efficient deuterium incorporation even with up to 50% by volume H₂O in the reaction solution due to the differential bond strengths in DMF and H₂O.²² Sonogashira cross-coupling reaction of 4 and 4-t-butyl-2-ethynylaniline²⁴ afforded 5 in 45% yield. Subsequent addition with 4-methoxyphenyl isocyanate gave 2^D in 34% yield. Compound 2^D and intermediates were characterized through ¹H, ²H, ¹³C{¹H}, and ¹⁹F NMR spectroscopy and high-resolution mass spectrometry (see ESI^†).Open in a separate windowScheme 1Synthetic route for the selective deuteration of anion receptor 2^D.Previous work on the DEIE of Cl⁻ binding with 1^H/D in DMSO revealed an experimental isotope effect of 1.019 ± 0.010. Therefore, we expected similar small DEIEs for HS⁻, Cl⁻, and Br⁻ binding with 2^H/D. Typical methods to determine binding constants (K_a) in supramolecular systems use non-linear regression fitting of titration data. Results from this method can be affected by small errors in the known initial host and guest concentration, quality of the titration isotherm, and subsequent data fitting, which when taken together often results in 2–15% errors in K_a. To increase the precision in K^H_a/K^D_a data for this study, we used the Perrin method of competitive titrations,²⁵ which has been shown previously to reduce errors in EIE values significantly with errors as small as 0.0004.²⁶ In this method, a linearized plot of the chemical shifts of 2^H (δ_H) and 2^D (δ_D) in fast exchange with an anionic guest is fit by linear regression to eqn (1):(δ⁰_H − δ_H)(δ_D − δ^f_D) = DEIE(δ⁰_D − δ_D)(δ_H − δ^f_H)1The slope of the linear regression is equal to the DEIE of the system. Because the linear regression only relies on chemical shift values and is independent of host and guest concentration, the precision of the method is limited to the precision of the NMR instrument and quality of data fitting.In addition, ¹³C NMR spectroscopy is sensitive to isotopic labelling and can show changes in chemical shifts between isotopomers. We were able to differentiate between the ¹³C NMR signals for C^ab, C¹ and C² for free and bound 2^H and 2^D (Fig. 2a) in 10% DMSO-d₆/CD₃CN, which were similar to those reported for 1^H/D in DMSO-d₆.¹² Competitive ¹³C NMR spectroscopy titrations were performed in anaerobic and anhydrous 10% DMSO-d₆/CD₃CN at 25 °C with mixtures of 2^H and 2^D in combined concentrations between 5.71 and 13.46 mM. Aliquots of the tetrabutylammonium (TBA) salts of HS⁻, Cl⁻, and Br⁻ were added until the system had reached saturation (Titration method A in ESI^†). In an effort to decrease reactivity of HS⁻ with 2^H/D and DMSO over long periods of time and decrease oxygen and water contaminations, some titrations with HS⁻ were performed by splitting the host solution of 2^H/D between four J-young NMR tubes. For each point in the competitive titration, TBASH was added to a new solution of 2^H/D inside an N₂-filled glovebox shortly before obtaining a ¹³C NMR spectra (Titration method B in ESI^†). The C^ab, C¹ and C^{2 13}C NMR signals were tracked for 2^H and 2^D in each titration for each anion. A representative competitive titration and linearized plots for Cl⁻ binding is shown in Fig. 2.Open in a separate windowFig. 2(a) Representation of the host–guest equilibrium between 2^H/D and Cl⁻. (b) Differences in the chemical shifts between the 2^H and 2^D isotopologues are observed in the ¹³C NMR signals for the C^ab, C¹, and C² carbons. ¹³C NMR signals for the C^ab, C¹, and C² carbons in 2^H and 2^D are tracked throughout a titration. (c–e) Linearized plots from fitting the chemical shifts of the C^ab, C¹, and C² throughout a titration to eqn (1).The DEIE data calculated from tracking the chemical shifts of the C^ab, C¹ and C^{2 13}C NMR signals from Cl⁻ and Br⁻ binding are summarized in eqn (1) through linear regression is included in parentheses

Enhanced phosphate removal by zero valent iron activated through oxidants from water: batch and breakthrough experiments

In this study, oxidants including hydrogen peroxide (H₂O₂), hypochlorite (ClO⁻) and persulfate (S₂O₈²⁻) were employed to promote zero-valent iron (ZVI) corrosion and enhance phosphate (P) removal from water through batch and breakthrough experiments. Characterization results indicated that the addition of oxidant can cause large-scale corrosion of the iron surface. This subsequently generates more iron ions and active minerals, resulting in a large number of reaction-adsorption sites for P removal. Therefore, compared with the ZVI alone system (29.4%), the removal efficiency of P by oxidant/ZVI system (H₂O₂ : ClO⁻ : S₂O₈²⁻ = 33.2% : 54% : 67.1%) was improved. For the oxidant/ZVI system, H₂O₂ can promote the corrosion of ZVI to a certain extent. However, the solution pH could be increased during the corrosion process. This leads to inhibition of P removal performance by the H₂O₂/ZVI system, which only increased by 12.9% to 33.2%. The reaction between NaClO and ZVI consumes less H⁺, and the reaction product Cl⁻ can pierce the passivation layer on the surface of the ZVI through the pitting effect. As such, the NaClO/ZVI system attained a 54% P removal rate. Compared with H₂O₂ and NaClO, a better P removal effect of about 67.1% can be achieved by using Na₂S₂O₈, since the oxidation corrosion process of Na₂S₂O₈ does not consume H⁺, and it also has the strongest oxidizing properties. Furthermore, an appropriate increase in oxidant dosing (0.1–2 mM) could improve the efficiency at which of P is removed. Five batch cycle experiments showed that the oxidant/ZVI system has a higher removal capacity and longer life-span. In the long-term column running, the P removal capacity and operation life of the NaClO/ZVI column are 9.6 times and 3.2 times higher than that of the ZVI column, respectively. This work demonstrates that an oxidant/ZVI system can be an efficient method for P removal in water, which also provides a new idea for solving the problem of ZVI corrosion passivation.

This model is used to illustrate the enhanced P removal by oxidant stimulated ZVI.     

The corrosion behavior of 304 stainless steel in NaNO3–NaCl–NaF molten salt and vapor

Corrosion behavior of 304 stainless steel in molten NaNO₃–NaCl–NaF salt and NaNO₃–NaCl–NaF vapor has been studied at 450 °C. The results showed that the samples suffered weight loss, and surface oxides, i.e. Fe₂O₃ and FeCr₂O₄ characterized by XRD, were formed after corrosion. The surface oxide layer was about 1.1 μm in thickness after corrosion in molten NaNO₃–NaCl–NaF salt, which was relatively homogeneous and dense. Whereas, the distribution of surface oxides was not even, and a shedding phenomenon was observed after corrosion molten NaNO₃–NaCl–NaF vapor. This is mainly attributed to the existence of NO₂ and NO in the molten NaNO₃–NaCl–NaF vapor determined by thermogravimetric infrared spectroscopy, which affected the adherence between oxides and the matrix. Additionally, the corrosion rate of 304 stainless steel in molten NaNO₃–NaCl–NaF salt is almost close to that in solar salt, which demonstrates that the synergy influence of Cl⁻ and F⁻ on the rate of 304 stainless steel is not significant. This work not only enriches the database of molten salt corrosion, but provides references for the selection of alloy and molten salt in the CSP.

Surface micro-morphology of 304 SS before corrosion (a), after corrosion in molten NaNO₃–NaCl–NaF salt (b) and molten NaNO₃–NaCl–NaF vapor (c). (Local enlarged region of A1 (b-1), A2 (c-1) and A3 (c-2)).     

Reversible ammonia uptake at room temperature in a robust and tunable metal–organic framework

Ammonia is useful for the production of fertilizers and chemicals for modern technology, but its high toxicity and corrosiveness are harmful to the environment and human health. Here, we report the recyclable and tunable ammonia adsorption using a robust imidazolium-based MOF (JCM-1) that uptakes 5.7 mmol g⁻¹ of NH₃ at 298 K reversibly without structural deformation. Furthermore, a simple substitution of NO₃⁻ with Cl⁻ in a post-synthetic manner leads to an increase in the NH₃ uptake capacity of JCM-1(Cl⁻) up to 7.2 mmol g⁻¹.

Recyclable and tunable ammonia adsorption with JCM-1 and JCM-1(Cl⁻) at room temperature occurs reversibly without structural decomposition.     

Photolysis of sulfamethazine using UV irradiation in an aqueous medium

Although many studies have been focused on the photochemistry of antibiotics, the roles of reactive species in photolysis and the effects of dissolved substances on antibiotic photochemical behavior have been poorly examined. The photolytic behaviors of sulfamethazine (SMN) in pure water were investigated via adding different scavengers to quench the active species. Results showed that decomposition of the triplet-excited state of SMN (³SMN*) by direct photolysis was the main path of SMN photolysis in water. Moreover, self-sensitized SMN cannot be ignored during SMN photodegradation. The main photoproducts of SMN were identified by LC-MS/MS, which indicated that SMN could not be mineralized although the photolysis under UV was effective. The effects of Cl⁻, NO₃⁻, and fulvic acid (FA) (common substances in natural water) on SMN photolytic behaviors were also studied. The triplet-induced halogenation of SMN increases the ionic strength and reduces the ground state SMN; these are the primary causes of promotion of SMN photolysis by Cl⁻. More ˙OH produced in the presence of NO₃⁻ could promote SMN photolysis. Competitive absorption of photons of FA with SMN and ROS scavenged by FA were the main reasons for the inhibition of SMN photolysis. The research findings are helpful for further studies on the environmental risks of ACs in natural waters and promoting the development of AC pollution treatment technology.

The role of reactive species in SMN photolysis and the effects of dissolved substances on SMN photochemical behavior.     

Ready-to-use binder-free Co(OH)2 plates@porous rGO layers/Ni foam electrode for high-performance supercapacitors

In this work, an outstanding nano-structured composite electrode is fabricated through the co-deposition of Co(OH)₂ nanoplates and porous reduced GO (p-rGO) nanosheets onto Ni foam (NF). Through field emission scanning electron microscopy and transmission electron microscopy observations, it was confirmed that porous reduced graphene oxide sheets are completely wrapped by uniform hexagonal Co(OH)₂ plates. Due to the unique architecture of both components of the prepared composite, a high surface area of 234.7 m² g⁻¹ and mean pore size of 3.65 nm were observed for the Co(OH)₂@p-rGO composite. The constructed Co(OH)₂@p-rGO/NF composite electrode shows higher energy storage capability compared to that of Co(OH)₂/NF and p-rGO/NF electrodes. The Co(OH)₂/NF electrode shows specific capacitances of 902 and 311 F g^–1 at 5 and 30 A g^–1, while the Co(OH)₂@p-rGO/NF electrode delivers 1688 and 1355 F g^–1 under the same current loads, respectively. Furthermore, when the current load was increased from 1 to 30 A g^–1, 74.5% capacitance retention was observed for the Co(OH)₂@p-rGO/NF electrode, indicating its outstanding high-power capability, while the Co(OH)₂/NF electrode retained only 38.5% of its initial capacitance. The fabricated Co(OH)₂@p-rGO/NF//rGO/NF ASC device shows an areal capacitance of 3.29 F cm⁻², cycling retention of 91.2% after 4500 cycles at 5 A g⁻¹ and energy density of 68.7 W h kg⁻¹ at a power density of 895 W kg⁻¹. The results of electrochemical tests prove that Co(OH)₂@p-rGO/NF exhibits good performance as a positive electrode for use in an asymmetric supercapacitor device. The prepared porous composite electrode is thus a promising candidate for use in supercapacitor applications.

Fabrication mechanism of a ready-to-use Co(OH)2@p-rGO/NF electrode: (a) base generation step, (b) electrophoretic deposition of rGO onto NF and (c) chemical formation of Co(OH)2 on rGO.     

Extraction of polyoxotantalate by Mg–Fe layered double hydroxides: elucidation of sorption mechanisms

The extraction of Ta(v) as polyoxometallate species (H_xTa₆O₁₉^(8−x)−) using Mg–Fe based Layered Double Hydroxide (LDH) was evaluated using pristine material or after different pre-treatments. Thus, the uptake increased from 100 ± 5 mg g⁻¹ to 604 ± 30 mg g⁻¹, for respectively the carbonated LDH and after calcination at 400 °C. The uptake with calcined solid after its reconstruction with Cl⁻ or NO₃⁻ anions has also been studied. However, the expected exchange mechanism was not found by X-ray Diffraction analysis. On the contrary, an adsorption mechanism of Ta(v) on LDH was consistent with measurements of zeta potential, characterized by very negative values for a wide pH range. Moreover, another mechanism was identified as the main contributor to the uptake by calcinated LDH, even after its reconstruction with Cl⁻ or NO₃⁻: the precipitation of Ta(v) with magnesium cations released from MgO formed by calcination of the LDH. This latter reaction has been confirmed by the comparison of the uptake of Ta(v) in dedicated experiments with solids characterized by a higher magnesium solubility (MgO and MgCl₂). The obtained precipitate has been analyzed by X-ray diffraction (XRD) and would correspond to a magnesium (polyoxo)tantalate phase not yet referenced in the powder diffraction databases.

Reaction of polyoxotantalate ions and MgFe Layered Double Hydroxide leads to magnesium polyoxotantalate precipitate.     

Multi-ionization of the Cl2 molecule in the near-infrared femtosecond laser field

The multi-electron ionization and subsequent dissociation of the Cl₂ molecule in a near-infrared femtosecond laser field was investigated via the dc-sliced ion imaging technique. The single charged molecular ions, Cl₂⁺, dissociate from two excited states, ²Π_u and ²Σ_g⁺, with the electrons ionized from the HOMO−1 and HOMO−2 orbital, respectively. For the multi-charged molecular ions, Cl₂ⁿ⁺ (n = 2–8), our results showed that the stretch of the inter-nuclear distance benefitted the ionization of the electrons to produce highly-charged molecular ions. In addition, compared with the traditional charge resonance enhanced ionization (CREI) model, the critical distance (R_c) for the Cl₂ molecule in our experiment was a short range that depended on the charge state rather than a single point.

The multi-electron ionization and subsequent dissociation of the Cl₂ molecule in a near-infrared femtosecond laser field was investigated via the dc-sliced ion imaging technique.     

Co(OH)F nanorods@KxMnO2 nanosheet core–shell structured arrays for pseudocapacitor application

In this work, Co(OH)F nanorods@K_xMnO₂ nanosheet core–shell nanostructure was assembled on Ni foam by a facile hydrothermal method and incorporated with an electrodeposition process. Benefiting from their core–shell nanostructure and heterogeneous nanocomposites, the arrays present high areal capacitance up to 1046 mF cm⁻² at 1 mA cm⁻² and display a remarkable specific capacitance retention of 118% after 3000 cycles. When the current density increases to 10 mA cm⁻², the capacitance is 821 mF cm⁻² displaying a good rate capability. The excellent electrochemical properties allow them to be used as a promising electrode material for pseudocapacitors and display wide application potential in the field of electrochemical capacitors.

In this work, Co(OH)F nanorods@K_xMnO₂ nanosheet core–shell nanostructure was assembled on Ni foam by a facile hydrothermal method and incorporated with an electrodeposition process.     

Temperature–humidity dual regulation of a single-core–double-shell microcapsule fabricated by electrostatic-assembly and chemical precipitation

Humidity and temperature control materials have attracted increasing attention due to their energy saving and intelligent regulation of human comfort in the field of interior building and clothing. Phase change microcapsules have been widely used, however, most of which focus on temperature regulation without humidity control. In this work, we report a novel temperature–humidity dual regulation microcapsule with single-core–double-shell structure. FT-IR and XRD measurements confirmed that the shell materials were successfully fabricated on the paraffin core via electrostatic-assembly and the subsequent chemical precipitation method. SEM, TEM and optical microscope photos showed that the microcapsules were spherical morphology with layer-by-layer shells at a diameter around 2–5 μm. The SiO₂ shell was aggregated from nano-sized particles and formed a loose and porous micro-structure, supported by the result of N₂ adsorption–desorption isotherms. In addition, the synergistic effect of hydrophilic and porous loose (chitosan/GO/chitosan)–SiO₂ double shells endowed the microcapsules with humidity regulation. The constructed microcapsules showed temperature regulation behavior due to its phase change performance of paraffin and good thermal durability after 10 thermal cycles. They also showed stable humidity regulation performance after repeated adsorption/desorption. The simulation experiments of temperature and humidity regulation indicated that the microcapsule could keep the temperature and humidity in a stable range. The as-prepared microcapsules have outstanding temperature and humidity regulation properties, showing an application prospects in energy-saving fields.

A single-core–double-shell microcapsule with temperature–humidity dual regulation was achieved by artfully designing of core and shell to realize the multi-functional and multi-factors regulation.     

Eco-friendly synthesis of ionic helical polymers and their chemical properties and reactivity

Reaction of N-(2,4-dinitrophenyl)pyridinium chloride (salt(Cl⁻)) with sodium dicyanamide (Na(CN)₂N) resulted in anion exchange between Cl⁻ and (CN)₂N⁻ to yield a new Zincke salt, salt((CN)₂N⁻). Reactions of salt((CN)₂N⁻) with piperazine, specifically (R)-(−)- or (S)-(+)-2-methylpiperazine under eco-friendly conditions, such as in aqueous solution, in the absence of a catalyst, and at room temperature, resulted in pyridinium ring opening to yield ionic high-molecular-weight polymers with 5-2,4-dienylideneammonium dicyanamide units or chiral 5-(2-methylpiperazinium)-2,4-dienylideneammonium dicyanamide units, namely, polymer(H;(CN)₂N⁻), polymer(R-Me;(CN)₂N⁻), and polymer(S-Me;(CN)₂N⁻). UV-Vis measurements revealed that the π-conjugation system expanded along the polymer chain due to the orbital interaction between the electrons on the two nitrogen atoms of the piperazinium ring. Circular dichroism (CD) measurements revealed a helical conformation of the main chain in polymer(R-Me;(CN)₂N⁻) and polymer(S-Me;(CN)₂N⁻). The reaction of polymer(H;(CN)₂N⁻) with p-phenylenediamine (PDA) caused recyclization of the 2,4-dienylideneammonium unit and resulted in depolymerization to yield N-(4-aminophenyl)pyridinium dicyanamide. Cyclic voltammetry analysis suggested that the polymers obtained in this study undergo electrochemical oxidation and reduction.

Reactions of salt((CN)₂N⁻) with (R)-(−)- or (S)-(+)-2-methylpiperazine under eco-friendly conditions resulted in a yield of ionic helical polymers.