Heavy Metal Complexes Research Articles

Dual Electroactivation of Peroxymonosulfate for Heavy Metal Complexes Decomplexation and Simultaneous Resource Recovery

Dual Electroactivation of Peroxymonosulfate for Heavy Metal Complexes Decomplexation and Simultaneous Resource Recovery

Patternable and flexible thermoelectric generators based on Bi2Te3/silk fibroin composites for temperature sensing and wearable applications

Thermoelectric (TE) materials are functional materials that can directly convert heat energy into electrical energy, and have a positive effect on alleviating the energy crisis. Inorganic semiconductor materials have attracted extensive attention due to their excellent TE properties, among which Bi2Te3 is the best and most widely used inorganic TE material at room temperature. However, inorganic TE materials are still restricted by unfavorable factors such as scarcity of raw material resources, heavy metal pollution, high price, high rigidity, and complex processing technology, which greatly limit their development process. Therefore, it is urgent to develop flexible TE materials with high performance, non-polluting, non-toxic and low price. The combination of silk fibroin and inorganic TE materials not only retains the properties of TE materials, but also improves their flexibility. Here, the Bi2Te3/SF TE films are successfully fabricated by the evaporation-assisted self-assembly method with Seebeck coefficient of 199 μV⋅K−1 (p-type) and −240 μV⋅K−1 (n-type). In order to verify the feasibility of collecting and utilizing ambient heat energy in real life, the Bi2Te3/SF TE films are cut into various patterns (such as, flower, rabbit, tree, etc) to collect wasted ambient heat. Further, the Bi2Te3/SF thermoelectric generator (TEG) reaches a maximum power of 21 nW at a temperature difference of 43.5 K. A series of self-power temperature sensing demonstrations from single TE film, TEG, to TEG array are proposed to demonstrate their potential applications in the field of self-power sensors. Finally, by inserting Bi2Te3/SF TEG array into a bracelet, a self-powered smart bracelet can be successfully constructed, demonstrating the feasibility of the Bi2Te3/SF TE film in the development of self-powered wearable electronics.

Advanced electrochemical oxidation of EDTA-Ni via cobalt single-atom catalysts: Exploring indirect persulfate activation pathways

This study explores an innovative electrochemical strategy for the removal of the highly stable and toxic EDTA-Ni complex found in electroplating wastewater. Utilizing a cobalt-based single-atom catalyst (Co-NC) in an electro-enhanced system, we achieved significant activation of peroxydisulfate (PDS) for effective degradation of EDTA-Ni. Under optimal conditions of 40 mA current density and a pH range of 3–7, more than 97% of EDTA-Ni (1 mM) was successfully degraded within 90 min. Through detailed electrochemical experiments, we identified that atomic hydrogen (H*) played a crucial role in the indirect activation of PDS, facilitating the formation of reactive sulfate radicals (·SO4-). Computational analysis using density functional theory (DFT) confirmed that the H*-mediated reduction pathway had a notably low energy barrier (ΔGbs = 0.51 eV), making it the dominant activation mechanism. Gas chromatography-mass spectrometry (GC–MS) further revealed the primary degradation intermediates, providing insights into the breakdown process of EDTA-Ni. This research underscores the potential of Co-NC catalyst as a highly effective catalyst for treating persistent heavy metal complexes in advanced oxidation systems.

Boron/Fe2+/H2O2 combined with resins process cost-effectively remove Ni(II) in wastewater containing Ni-EDTA: Performance and mechanism

This study proposes a green purification strategy in which mild decomplexation of Ni-EDTA into other Ni complexes facilitates the efficient removal and recovery of nickel through resin adsorption. Decomplexation of Ni-EDTA by boron/Fe2+/H2O2 (B/Fe2+/H2O2) followed by resins adsorption was conducted for Ni(II) removal in Ni-EDTA. The Ni(II) removal efficiency could only achieve 1.3 % and 6.2 % while Ni(II) coexisted with EDTA but more than 10 times of higher when Ni(II) coexisted with EDTA-relatives via the single adsorption of commercial heavy metal-affined resins (D001 and D463), which attributed to the increased binding energies of these Ni-EDTA’s degradation products complexes than Ni-EDTA based on density functional theory (DFT) calculation. In comparing to precipitation, the resin adsorption required much less mineralization of EDTA to have a better removal efficiency of Ni(II). B improved the efficiency of Ni-EDTA decompexation by accelerating the recycle of Fe3+/Fe2+. The EDTA (and TOC) removal enhanced from 48.7 % (4.7 %) to 94.7 % (11.9 %) by B/Fe2+/H2O2 process comparing to Fe2+/H2O2 process. With the high EDTA but low TOC removal efficiency after B/Fe2+/H2O2 treatment, Ni(II) removal efficiency via resins adsorption could maximum achieve 80.5 %, 2–3 times of that via regular precipitation method. In addition, B and resins exhibited good reusability in five cycles, and B/Fe2+/H2O2-resins process had excellent adaptability to different heavy metal complexes. B/Fe2+/H2O2-D463 system not only could reduce 78.4 % reagents cost compared with that of Fe2+/H2O2-precipitation process, but also could save much cost than other processes. The results provide new insights for the cost-effective treatment of EDTA-complexed heavy metal wastewater.

Cu(Ⅱ)-EDTA degradation and copper recovery from wastewater in wide pH ranges by an electrooxidation-capacitive deionization system

The treatment and recovery of metal resources from complex industrial wastewater has posed significant challenges due to the presence of multiple heavy metal ions, heavy metal complexes, and acidic conditions. In this study, a novel electrooxidation-capacitive deionization (EO-CDI) system was proposed, which ingeniously harnessed the unheeded Faraday side reaction in capacitive deionization for simultaneous degradation and recovery of copper complexes from wastewater through two electrode integration. Specially, the cathode CuS0.78Se0.22 synthesized through the anionic Se-substitution strategy exhibited a remarkable adsorption capacity up to 672.02 mg/g for Cu ions, outstanding selectivity and stability, particularly in acidic environments. The water oxidation process occurring at the activated carbon anode played a crucial role by generating active species that contribute to the degradation of Cu(Ⅱ)-EDTA, which leaded to the release of copper ions, facilitating their subsequent recovery. Cyclic experiments further confirmed the excellent cyclic stability of the hybrid EO-CDI system, along with its impressive performance in copper extraction when applied to real industrial wastewater. This innovative approach offered promising prospects for addressing the challenges associated with the treatment of complex industrial wastewater and the recovery of valuable metal resources.

Assessing the complexation of dissolved organic matter with heavy metals (Cu2+, Pb2+) in leachate from an old Japanese landfill site using fluorescence quenching.

Dissolved organic matter (DOM) in landfill leachate impacts the toxicity, bioavailability, and migration of heavy metals. The present study investigated the complexation of heavy metals (Cu2+ and Pb2+) with DOM from two landfill leachate samples, representing an old landfill site containing incineration residues and incombustible waste. The logarithms of the stability constant (log KM) and percentage of complexed fluorophores were calculated using both the Ryan-Weber non-linear model and the modified Stern-Volmer model, yielding good agreement. The log KM values (at pH = 6.0 ± 0.1) calculated using both methods for the two sampling points were 5.02-5.13 and 4.85-5.11 for Cu2+-DOM complexation, and 5.01-5.13 and 4.46-4.87 for Pb2+-DOM complexation, respectively. Log KM was slightly higher for binding of DOM with Cu2+ than Pb2+, and the quenching degree was stronger for complexation with Cu2+ (28.5-30.6% and 38.0-45.9%) than Pb2+ (6.5-7.1% and 10.0-15.4%) in both leachate samples. While log KM values were similar, differences in the contributions of functional groups and molecular composition led to varying degrees of quenching. This study reveals the potential for heavy metal binding by DOM in landfill leachate with a unique solid waste composition and emphasizes variations in fluorescence quenching between Cu2+ and Pb2+ despite similar log KM levels. These findings may be useful for assessing heavy metal behavior in landfill leachate and its impacts on the surrounding environment.

Mechanistic Insights into Micelle-Enhanced Nanofiltration for Heavy Metal Removal: Transformation of Ion Transport and Fouling Phenomena.

Toxic heavy metals are widely present in typical scenarios, such as mines and electroplating wastewater, presenting significant risks to biological and environmental safety. Membrane processes encounter a challenge in effectively intercepting heavy metals due to their small hydration radius. This research showcases the high efficiency of micelle-enhanced nanofiltration (MENF) in removing heavy metals. At the critical micelle concentration, sodium dodecyl sulfate demonstrated a high removal of Cu2+, Ni2+, Zn2+, and Cd2+ while maintaining substantial potential for complexation of heavy metals. The formation of micelles and the bonding of heavy metals with surfactants bolstered the resistance of heavy metal ions to transmembrane transport. The presence of heavy metals in ionic form in wastewater facilitated their complexation with surfactants or micelles. Notably, the valence state and concentration of interfering ions in the environment could slightly influence the removal of heavy metals by MENF. Additionally, MENF displayed remarkable antifouling properties. The loose gel layer created by surfactant molecules and the micelle enhanced the membrane permeability and reduced the scaling tendency of heavy metals. This study contributes to an improved understanding of the mechanisms involved in heavy metal rejection by using MENF.

Autocatalytic degradation of Cu-EDTA in the Calcite/PMS system: Singlet oxygen and Cu(III)

The simultaneous removal of heavy metal complexes (HMCs) and heavy metal ions presents a significant challenge in treating wastewater. To address this, we propose a Calcite/Peroxymonosulfate (Calcite/PMS) system aimed at simultaneously decomplexing Cu-EDTA and removing Cu ions. Calcite/PMS system could achieve 99.5 % Cu-EDTA decomplexation and 61.9 % Cu ions removal within 60 min under initial conditions of Cu-EDTA (10 mg/L), Calcite (3 g/L), and PMS (2 mM). Singlet oxygen (1O2) emerged as the predominant reactive species responsible for Cu-EDTA decomplexation, which selectively targeted the N-C bonds in the Cu-EDTA structure to produce intermediates with lower biotoxicity than EDTA. Interestingly, solid phase Cu(III) (≡Cu(III)) promoted the generation of superoxide radicals (O2•−) with a contribution of up to 72.8 %. Subsequently, nascent ≡Cu(III) and O2•− accelerated the degradation of intermediates. Besides, coexisting organic substances inhibited Cu-EDTA decomplexation, whereas inorganic ions had a weak impact. After five cycles of use, the Calcite/PMS system retained 99.3 % efficiency in decomplexing Cu-EDTA. This investigation provides valuable insights into using calcite to remove HMCs and enhances our comprehension of the decomplexation intermediates accelerating HMCs degradation.

Tanning wastewater restructured nitrogen-transforming bacteria communities and promoted N2O emissions in receiving river riparian sediments

Physicochemical and toxicological characterization of leather tanning wastewater has been widely documented. However, few reports have examined the response of denitrification N2 and N2O emissions in riparian sediments of tannery wastewater-receiving rivers. In this study, 15N-nitrate labeling was used to reveal the effects of tanning wastewater on denitrification N2 and N2O emission in a wastewater-receiving river (the old Mang River, OMR). OMR riparian sediments were highly polluted with total organic carbon (93.39 mg/kg), total nitrogen (5.00 g/kg) and heavy metals; specifically, Cr, Zn, Cd, and Pb were found at concentrations 47.3, 5.8, 1.6, 4.3, and 2.8 times that in a nearby parallel river without tanning wastewater input (the new Mang River, NMR), respectively. The denitrification N2 emission rates (0.0015 nmol N · g−1 h−1) of OMR riparian sediments were significantly reduced by 2.5 times compared with those from the NMR (p < 0.05), but the N2O emission rates (0.31 nmol N · g−1 h−1) were significantly increased (4.1 times, p < 0.05). Although the dominant nitrogen-transforming bacteria phylum was Proteobacteria in the riparian sediments of both rivers, 11 nitrogen-transforming bacteria genera in the OMR were found to be significantly enriched; five of these were related to pollutant degradation based on linear discriminant analysis (LDA >3). The average activity of the electron transport system in the OMR was 6.3 times lower than that of the NMR (p < 0.05). Among pollution factors, heavy metal complex pollution was the dominant factor driving variations in N2O emissions, microbial community structure, and electron transport system activity. These results provide a new understanding and reference for the treatment of tanning wastewater-receiving rivers.

Preparation of electrospun cellulose acetate/chitosan membranes for efficient sorption of heavy metals from aqueous solutions

Guided by efficient utilization of natural abundant cellulose and chitosan as separation materials, it is desired to tailor the composition of electrospun cellulose acetate/chitosan (CL/CS) membranes to achieve their optimal application in the management of aquatic heavy metal pollution. In this work, CL/CS membranes with enhanced surface area of 11.3–38.6 m2/g were successfully fabricated via electrospinning technique by dissolving cellulose acetate and chitosan into the environmental-friendly electrospinning solvent of LiOH/thiourea/H2O. Electrospun CL/CS membranes allowed the efficient sorption of Cr(VI), Pb(II) and Cu(II) with favorable kinetics (8.0 h), and excellent capacities (127.6 mg/g for Cr(VI), 66.2 mg/g for Pb(II), 46.7 mg/g for Cu(II) at pH 5.0, T 298 K). Meanwhile, they presented favorable efficiencies in the removal of these multiple heavy metals from acid simulated wastewaters. The spectroscopic analysis results indicated that the sorption mechanism should be dominant by the surface complexation of heavy metals with hydroxyl O-/amino N-species, the electrostatic attraction (protonated NH3+ with negatively charged HCrO4-, deprotonated O- with positively charged Pb(II) and Cu(II)), as well as the reduction of Cr(VI) to Cr(III) by surface reductive N-species. This work demonstrated the feasibility of electrospun CL/CS membranes as a promising choice for the remediation of aquatic heavy metals.

Distribution Characteristics, Risk Assessment, and Source Analysis of Heavy Metals in Farmland Soil of a Karst Area in Southwest China

Soil environmental quality related to the residents’ life, health, and safety, has been the hotspot issues in science of ecological environment protection. Evaluating the distribution characteristics, ecological risk, and source of heavy metals in farmland is important for protecting soil resources. The agricultural area of Lianhua town, Gongcheng County, Guilin is a typical karst landform. In response to the problem of heavy metal pollution and complex sources in the soil of this area, the characteristics and sources of heavy metal pollution in the soil profiles from farmland, abandoned land, and forest were studied using the single-factor index method, the geoaccumulation index (Igeo) principal component analysis (PCA) and positive matrix factorization (PMF) model. The results showed that: (1) that the contents of cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni), lead (Pb), and zinc (Zn) in the soil profile of the study area were higher than that of the soil elements background values in Guangxi. The total and available forms contents of all heavy metal elements exhibited the characteristics of accumulation in the surface profile; (2) among the six heavy elements, the contents of Cd were in a moderately to heavily polluted state. The contents of Cd in some soil profiles exceeded the control standard for agricultural land soil pollution. The contents of Zn and Ni were from slightly to moderately polluted in areas with frequent agricultural activities; (3) according to the PCA and PMF model, there were three main sources of heavy metals in the study area. Among them, Cd, Cu, Ni, and Zn are related to agricultural activities; the elements As, Cd, Cr, and Hg are closely related to geological background; Pb and Zn are mainly affected by atmospheric sedimentation of transportation. Agricultural activities and natural geological background are the main contribution sources of heavy metals in soil. Human activities are the main factors that cause the accumulation of heavy metals in soil. This research has theoretical guidance and practical significance for the prevention and control of soil heavy metal pollution and the protection of farmland environmental quality in the region.

One-step rapid removal of Cu(II) complexes via dual-active-site MOF catalysis with Peroxymonosulfate: Cooperative oxidation and adsorption

The removal of heavy metal complexes (HMCs) from wastewater is challenging due to their structural stability. Traditional methods require advanced oxidation processes (AOPs) for decomplexation, followed by chemical precipitation or adsorption. This study proposes a one-step approach using Co-imidazolate zeolitic framework-67 (ZIF-67) for simultaneous oxidation-decomplexation and in-situ adsorption of HMCs. The ZIF-67/peroxymonosulfate (PMS) system achieves 97.8 % removal of Cu(II)-citric acid complex (Cu-CA) in 60 mins, even under alkaline conditions, and demonstrates strong selectivity against ions like Ca, Mg, Na, and humic acid (HA). It effectively treats various contaminated water sources, achieving over 90 % removal efficiency for Cu(II) complexes such as oxalic acid (OA) and ethylenediaminetetraacetic acid (EDTA). The mechanism involves sulfate radicals (SO4•−) and singlet oxygen (1O2) for decomplexation, followed by amine groups in MOFs capturing Cu(II) ions through coordination interactions. This work offers a straightforward one-step method for HMCs contamination mitigation.

Combination of TiCl3 reduction/coagulation and ceramic membrane filtration for heavy metal complex removal

Ni-EDTA is a common heavy metal complex found in electroplating wastewater. As heavy metal complexes are stable and highly toxic, it is essential to develop efficient strategies to remove. In this work, TiCl3 coagulation and ceramic microfiltration membrane were combined in the removal of Ni-EDTA. Based on the results, this combinative process exhibited a high Ni-EDTA removal efficiency. When compared to employing the TiCl3 coagulation process only, the combinative process improved Ni2+ and TOC removal efficiencies from 91 % to 97 % and from 60 % to 93 %, respectively. Furthermore, it was found that the in-situ formed titanium hydrolysates possessed good adsorption for EDTA and Ni-EDTA, with maximum capacities reaching 713 mg/g and 213 mg/g, respectively, which also enabled the cake layer a considerable secondary removal for TOC. Mechanistic investigations confirmed that the reducibility of Ti3+ contributed to both Ni-EDTA and EDTA removal. In the presence of Ti3+, Ni-EDTA was decomplexed and the released Ni2+ was reduced to Ni0 synchronously. Meanwhile, some dissociated EDTA would combine with oxidized Ti4+ to form Ti-EDTA and ultimately promote the formation of TiO2 crystals. The formation of the insoluble chelate Ti-EDTA and the adsorption by surface hydroxyl of TiO2 were the key reasons for the efficient removal for released EDTA. This work provides a new approach for the decomplexation and harmless separation of heavy metal complexes.

Remediation effect of walnut shell biochar on Cu and Pb co-contaminated soils in different utilization types

Biochar, with its dual roles of soil remediation and carbon sequestration, is gradually demonstrating great potential for sustainability in agricultural and ecological aspects. In this study, a porous biochar derived from walnut shell wastes was prepared via a facile pyrolysis coupling with in-situ alkali etching method. An incubation study was conducted to investigate its performance in stabilizing copper (Cu) and lead (Pb) co-contaminated soils under different utilization types. The biochar effectively decreased the bioavailable Cu (8.5–91.68%) and Pb (5.03–88.54%), while increasing the pH, CEC, and SOM contents in both soils. Additionally, the results of sequential extraction confirmed that biochar promoted the transformation of the labile fraction of Cu and Pb to stable fractions. The mechanisms of Cu and Pb stabilization were found to be greatly dependent on the soil types. For tea plantation yellow soil, the main approach for stabilization was the complexation of heavy metals with abundant organic functional groups and deprotonation structure. Surface electrostatic adsorption and cation exchange contributed to the immobilization of Cu and Pb in vegetable-cultivated purple soil. This research provides valuable information for the stabilization of Cu and Pb co-contaminated soils for different utilization types using environmentally-friendly biochar.

ENVIRONMENTAL ASSESSMENT OF SOIL STATE IN THE IMPACT ZONE OF THE SREDNEURALSKY COPPER SMELTER

As part of the study of the ecological state of soils and vegetation in the zone of impact of the Sredneuralsky Copper Smelter (SUMZ), the following tasks were solved: the content of heavy metals in the soils of the test sites laid within the zone of impact of the SUMZ was determined; macrokinetic patterns of seasonal dynamics of the normalized relative vegetation index (NDVI) at the test sites in the zone of impact of the SUMZ were revealed; macrokinetic patterns of vegetation response in the form of NDVI, calculated according to MODIS and Landsat 8 data, to soil pollution by a complex of heavy metals in the zone of impact of the SUMZ were revealed; soil quality was ranked according to the patterns of vegetation response in the form of NDVI to soil pollution by a complex of heavy metals within the boundaries of the natural protection zone (NZZ) of the SUMZ according to 2023. The intra-seasonal dynamics of photosynthetically active biomass in the form of NDVI was modeled using a theoretical growth equation based on MODIS satellite data. The seasonal maximum of the vegetation index at the trial sites in 2012 fell on the 25-28 week. In 2023, it occurred on the 27-33 week, depending on the location of the sampling point. The rate of maximum achievement is characterized by weak intra-seasonal and interannual variation. The patterns of changes in the concentration of photosynthetically active biomass in the form of maximum NDVI for the 2023 season in response to the gross content of a complex of heavy metals (Cu, Pb, Cd and Zn) in the soil of the test sites were modeled using the theoretical equation of dose dependence. The maximum permissible level of the heavy metal complex in the soil in the form of a geometric mean, which does not cause a decrease in the values of the vegetation index calculated according to the data of the MODIS and Landsat 8 satellites, was 101 and 106 mg·kg-1, respectively. The analysis of histograms of the distribution of NDVI values within the NZZ was carried out, which showed how the true frequencies of occurrence of the values of the vegetation index correspond to the empirical boundary of the NZZ associated with the maximum dose dependence point identified by the study of the 2012. The nature of the distribution of true NDVI values for the NZZ exclusively fully supports the used zoning theory based on the analysis of dose dependence. The modern boundaries of the SUMZ natural protection zone are 4-7 km away from the center of the sanitary protection zone.

Determination of Binding Constants for the Complexes Between Heavy Metal Ions and Cucurbit[n]uril

AbstractOne of the major concerns worldwide is the rapid increase in water pollution with hazardous heavy metals. The Cucurbit[n]uril (CB[n]) structure provides an inner hydrophobic cavity accessible through two electrostatically negative portals with polar carbonyl groups, allowing for charged ion–dipole interaction between cationic species with excellent binding affinities. In this work we selected CB[5], and CB[7] for the titrimetric and electrochemical evaluation of the heavy metal complexes formed with Copper(II), Cadmium(II) and Lead(II). The host–guest interaction was found by either attenuation of the redox peaks, the formation of a new peak, or the slight shift in the redox peaks of the heavy metal ions. Titration data were obtained for CB[n] with the heavy metal solutions to determine the molar coefficient of binding. The stoichiometry of the complexes was 1 : 1 by Job′s plot. We calculated the binding constants using the Benesi–Hildebrand method achieving relatively good binding constants (K) ranging from (1.80±0.14)×105–(4.98±0.13)×105 M−1. The results showed that the complexes of Cadmium(II) and Lead(II) with both CB[5] and CB[7] are highly stable in aqueous media. Copper(II) was able to bind to the smaller sized portal of CB[5], whereas with CB[7] the heavy metal ion could not form a favourable complex. This phenomenon suggests that the CB[5] is an ideal host at forming stable host–guest interactions than their larger homologue.

Unraveling the toxicity response and metabolic compensation mechanism of tannic acid-Cr(III) complex on alga Raphidocelis subcapitata

Due to their assembly properties and variable molecular weights, the potential biological toxicity effects of macromolecular organic ligand heavy metal complexes are more difficult to predict and their mechanisms are more complex. This study unraveled the toxicity response and metabolic compensation mechanism of tannic acid-Cr(III) (TA-Cr(III)) complex on alga Raphidocelis subcapitata using multi-omics approaches. Results showed TA-Cr(III) complex caused oxidative damage and photosystem disruption, destroying the cell morphology and inhibiting algal growth by >80 % at high exposure levels. TA-Cr(III) complex stress down-regulated proteins linked to proliferation, photosynthesis and antioxidation while upregulating carbon fixation, TCA cycle and amino acid metabolism. The increase of fumarate, citrate, isocitrate and semialdehyde succinate was validated by metabolomics analysis, which improved the TCA cycle, amino acid metabolism and carbon fixation. Activation of the above cellular processes somewhat compensated for the inhibition of algal photosynthesis by TA-Cr(III) complex exposure. In conclusion, physiological toxicity coupled with downstream metabolic compensation in response to Cr(III) complex of macromolecular was characterized in Raphidocelis subcapitata, unveiling the adaptive mechanism of algae under the stress of heavy metal complexes with macromolecular organic ligands.

Reversible Photoinduced Ligand Substitution in a Luminescent Chromium(0) Complex.

Light-triggered dissociation of ligands forms the basis for many compounds of interest for photoactivated chemotherapy (PACT), in which medicinally active substances are released or "uncaged" from metal complexes upon illumination. Photoinduced ligand dissociation is usually irreversible, and many recent studies performed in the context of PACT focused on ruthenium(II) polypyridines and related heavy metal complexes. Herein, we report a first-row transition metal complex, in which photoinduced dissociation and spontaneous recoordination of a ligand unit occurs. Two scorpionate-type tridentate chelates provide an overall six-coordinate arylisocyanide environment for chromium(0). Photoexcitation causes decoordination of one of these six ligating units and coordination of a solvent molecule, at least in tetrahydrofuran and 1,4-dioxane solvents, but far less in toluene, and below detection limit in cyclohexane. Transient UV-vis absorption spectroscopy and quantum chemical simulations point to photoinduced ligand dissociation directly from an excited metal-to-ligand charge-transfer state. Owing to the tridentate chelate design and the substitution lability of the first-row transition metal, recoordination of the photodissociated arylisocyanide ligand unit can occur spontaneously on a millisecond time scale. This work provides insight into possible self-healing mechanisms counteracting unwanted photodegradation processes and seems furthermore relevant in the contexts of photoswitching and (photo)chemical information storage.

Adsorption and enrichment of low-concentration heavy metal complexes by retractable claws made of polyelectrolyte brushes

The removal of heavy metal complexes from water at low concentrations poses a difficult challenge as the cost of chemical or energy input is often disproportional to the benefits gained. Herein, we propose a novel strategy by employing polyelectrolyte brushes as the “retractable claws” for adsorption and enrichment of heavy metal complexes. The polyelectrolyte brush constructed by grafting poly[2-(methacryloyloxy)ethyl trimethylammonium chloride] on the reduced graphene oxide (rGO-PMTC), exhibits a high adsorption capacity of 4.80 mg g−1 for 4.96 mg L−1 of Cu-ethylenediaminetetraacetic acid (Cu-EDTA), which is nearly 30 times larger than that of parent graphene oxide. Moreover, a very rapid adsorption rate can be achieved as 7.17 g mg−1 min−1, which is up to 3 orders of magnitude higher than many reported adsorbents. Molecular dynamics simulations reveal that during the adsorption process, the flexible polyelectrolyte brushes are fully extended to form the “claws” for quickly capturing Cu-EDTA complexes by strong electrostatic attraction. Subsequently, the polyelectrolyte brushes shrink with Cu-EDTA-mediated bridging and wrap the heavy metal complexes inside. In addition, the adsorbed Cu-EDTA complexes can be completely released from the polyelectrolyte brushes by simply introducing sodium chloride, resulting in an almost 20-fold enrichment of metal concentration for recycling. After ten adsorption–desorption cycles, the polyelectrolyte brushes only have 10 % reduction in the adsorption efficiency. The novel adsorbent can be extended to the effective removal of other heavy metal complexes with a low concentration and real electroplating wastewater.

Gold(I) complexes as powerful photosensitizers - a visionary frontier perspective.

Singlet oxygen production and its reactivity have significant implications in fields ranging from polymer science to photodynamic therapy. Extensive research has focused on the development of organic-based materials and heavy metal complexes, including Ru(II), Rh(III), Ir(III) and Pt(II). However, metal complexes containing Au(I) have been scarcely explored and warrant further investigation. This review provides a comprehensive analysis of reported compounds, classified based on the ligands coordinated to the gold(I) centre. Additionally, future directions in photosensitizer development and singlet oxygen applications are discussed.