Cyanides and Isocyanides of Zinc, Cadmium and Mercury: Matrix Infrared Spectra and Electronic Structure Calculations for the Linear MNC, NCMCN, CNMNC, NCMMCN, and CNMMNC Molecules.

Cadmium atoms from laser ablation react with cyanogen, NC=CN, in excess argon during co-deposition at 4 K, and even more on UV irradiation of the cold samples. Final annealing to 35 K increases bands at 2187.3 and 2089.2 cm-1 at the expense of weaker bands at 2194.6 and 2092.2 cm-1 through addition of another cadmium atom. Reaction products were identified by comparison with B3LYP and CCSD(T) computed frequencies and energies, through frequency differences between Zn and Cd products, and by cyanogen isotopic substitution. The CN radical, ZnNC, and CdNC were observed on sample deposition. Hg arc ultraviolet (UV) irradiation activates the insertion of Cd and Zn to form the NCCdCN, CNCdNC, NCZnCN and CNZnNC molecules. Next annealing increased the dimetal products NCCdCdCN, CNCdCdNC, NCZnZnCN, and CNZnZnNC at the expense of their single metal analogs. Laser ablated mercury amalgam also produced NCHgCN, NCHg-HgCN, CNHgNC and CNHg-HgNC. The Group12 metals form both cyanide and isocyanide products, and the argon matrix also traps the higher energy but much more intensely absorbing isocyanides. In the isocyanide case bond polarity results in very intense infrared absorptions. Group 12 metals produce shorter M-M bonds in the dimetal cyanides NCM-MCN and isocyanides CNM-MNC than in the M-M itself, and their computed M-M bond lengths compare favorably with those measured for dimetal complexes stabilized by large ring containing molecular ligands.

Highly Effective Removal of Metal Cyanide Complexes and Recovery of Palladium Using Quaternary-Ammonium-Functionalized MOFs.

In this study, quaternary-ammonium-functionalized metal⁻organic frameworks (MOFs) Et-N-Cu(BDC-NH2)(DMF), were prepared, characterized, and applied for the highly effective removal of metal cyanide complexes, including Pd(CN)4²-, Co(CN)6³-, and Fe(CN)6³-. Batch studies were carried out, and the maximum adsorption capacities of Pd(II), Co(III), and Fe(III) reached 172.9, 101.0, and 102.6, respectively. Adsorption was rapid, and equilibrium was established within 30 min. Et-N-Cu(BDC-NH2)(DMF) exhibited high thermal and chemical stability. Furthermore, absorbed Pd(CN)4²- was selectively recovered by two-step elution. First, Co(CN)6³- and Fe(CN)6³- were eluted with a 1.5 mol L-¹ KCl solution. Elution rates of Co(CN)6³- and Fe(CN)6³- were greater than 98.0%, whereas the elution percentage of Pd(CN)4²- was less than 2.0%. Second, >97.0% Pd(CN)4²- on the loaded MOFs was eluted using a 2.0 mol L-¹ KI solution. The recovery rate of Pd(CN)4²- was greater than 91.0% after five testing cycles. Adsorption isotherms, kinetics models, and adsorption thermodynamics of Pd(CN)4²- on Et-N-Cu(BDC-NH2) (DMF) were also systematically investigated. The Et-N-Cu(BDC-NH2) (DMF) absorbent exhibited a rapid, excellent ability for the adsorption of metal cyanide complexes.

The impact of gold mining activities: understanding the dynamics of cyanide in river ecosystems in Ecuador.

Understanding the behavior of cyanide in rivers is of utmost importance as it has a direct impact on the health of people who depend on these water sources. Cyanide contamination from gold mining activities poses a significant environmental threat to river ecosystems, particularly in southern Ecuador. This study aimed to investigate the behavior of cyanide when it enters contact with other metals in these rivers. Simulations were conducted to determine the speciation of cyanide, mercury, arsenic, lead, and manganese in a study area, taking into account the water temperature and pH at four locations. The findings revealed that CN-and HCN(aq) species were present in the research area. Additionally, mercury-cyanide (Hg(CN)2(aq), Hg(CN)3-), and manganese-cyanide (MnCN+) complexes were identified 3 km downriver from the site where the mining activity is higher. These metal-cyanide complexes tend to dissociate quickly under weak acidic conditions, making them hazardous to the environment. This research is crucial, not only for the environment but also for human health, as it allows to predict toxicity risks for people supplied with this water source, emphasizing the potential harm to human health. This study highlights the importance of stringent regulations and effective monitoring practices to mitigate cyanide contamination and safeguard environmental and occupational health.

Synthesis of Polyether, Poly(Ether Carbonate) and Poly(Ether Ester) Polyols Using Double Metal Cyanide Catalysts Bearing Organophosphorus Complexing Agents.

We developed a series of Zn(II)-Co(III) double metal cyanide (DMC) catalysts with exceptional activity for the ring-opening polymerization of various cyclic monomers by employing diverse organophosphorus compounds as complexing agents (CAs). The chemical structure and composition of DMC catalysts were investigated by commonly used analysis such as infrared and X-ray photoelectron spectroscopies, and elemental analysis combining with in situ NMR analysis to determine the complexation types of organophosphorus compounds the catalyst framework. The resulting catalysts exhibited very high turnover frequencies (up to 631.4 min-1) in the ring-opening polymerization (ROP) of propylene oxide and good efficiency for the ROP of ε-caprolactone. The resultant polyester polyols are suitable to use as an macroinitiator to produce well-defined poly(ester ether) triblock copolymers of 1800-6600 g mol-1 and dispersity of 1.16-1.37. Additionally, the DMC catalysts bearing organophosphorus compounds CAs exhibited remarkable selectivity for the copolymerization of PO with CO2, yielding poly(ether carbonate) polyols with carbonate contents up to 34.5%. This study contributes to the development of efficient DMC catalytic systems that enable the synthesis of high-quality polyols for various applications.

Sustainable Polycaprolactone Polyol-Based Thermoplastic Poly(ester ester) Elastomers Showing Superior Mechanical Properties and Biodegradability.

Thermoplastic elastomers (TPEs) have attracted increasing attention for a wide variety of industrial and biomedical applications owing to their unique properties compared to those of traditional rubbers. To develop high-performance engineering TPEs and reduce the environmental pollution caused by plastic waste, α,ω-hydroxyl-terminated polycaprolactone (PCL) polyols with molecular weights of 1000-4200 g mol-1 and polydispersity index (Ð) of 1.30-1.88 are synthesized via the ring-opening polymerization of sustainable ε-caprolactone using a heterogeneous double metal cyanide catalyst. The resulting PCL polyols are employed as soft segments to produce thermoplastic poly(ester ester) elastomers and are compared to conventional thermoplastic poly(ether ester) elastomers prepared from polytetramethylene ether glycol (PTMEG). Notably, the PCL-based TPEs exhibit superior mechanical properties and biodegradability compared to PTMEG-based TPEs owing to their crystallinity and microphase separation behaviors. Accordingly, they have 39.7 MPa ultimate strength and 47.6% biodegradability, which are much higher than those of PTMEG-based TPEs (23.4 MPa ultimate strength and 24.3% biodegradability). The introduction of biodegradable PCLs demonstrates significant potential for producing biodegradable TPEs with better properties than polyether-derived elastomers.

Old Materials for New Functions: Recent Progress on Metal Cyanide Based Porous Materials.

Cyanide is the simplest ligand with strong basicity to construct open frameworks including some of the oldest compounds reported in the history of coordination chemistry. Cyanide can form numerous cyanometallates with different transition metal ions showing diverse geometries. Rational design of robust extended networks is enabled by the strong bonding nature and high directionality of cyanide ligand. By virtue of a combination of cyanometallates and/or organic linkers, multifunctional framework materials can be targeted and readily synthesized for various applications, ranging from molecular adsorptions/separations to energy conversion and storage, and spin-crossover materials. External guest- and stimuli-responsive behaviors in cyanide-based materials are also highlighted for the development of the next-generation smart materials. In this review, an overview of the recent progress of cyanide-based multifunctional materials is presented to demonstrate the great potential of cyanide ligands in the development of modern coordination chemistry and material science.

Highly Active Heterogeneous Double Metal Cyanide Catalysts for Ring-Opening Polymerization of Cyclic Monomers.

A series of heterogeneous Zn-Co double metal cyanide (DMC) catalysts were investigated for ring-opening polymerization (ROP) of various cyclic monomers. Notably, inexpensive and commonly used organic solvents such as acetone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, nitromethane, and 1-methylpyrrolidin-2-one were very effective complexing agents for the preparation of DMC catalysts, showing high catalytic activity for the ROP of propylene oxide, ε-caprolactone, and δ-valerolactone. The chemical structures and compositions of the resultant catalysts were determined using various techniques such as FT-IR, X-ray photoelectron spectroscopy, powder X-ray diffraction, and elemental analysis. α,ω-Hydroxyl-functionalized polyether and polyester polyols with high yields and tunable molecular weights were synthesized in the presence of various initiators to control functionality. Kinetic studies of the ROP of δ-valerolactone were also performed to confirm the reaction mechanism.

Removal of metal-cyanide complexes and recovery of Pt(II) and Pd(II) from wastewater using an alkali-tolerant metal-organic resin.

Metal-cyanide complexes are hazardous and toxic pollutants that can accumulate in organisms, and their natural degradation is difficult. These complexes are primarily present in alkaline wastewater effluents, and an effective technique for their removal must be developed. Herein, we have successfully synthesized a novel quaternary ammonium-functionalized Zr4+ metal-organic resin (MOR) (H16[Zr6O16(MPATP)4]Cl8·xH2O, MPATP = 2-((1-methylpyridin-1-ium-2-ylmethyl)amino)-terephthalic acid), which we refer to as MOR-2-QAS. With alkali resistance, high surface area, and high anion exchange capacity, it acts by introducing positively charged pyridine into the organic ligand. The experimental results indicate that MOR-2-QAS becomes rapidly attached and efficiently removes Pt(CN)42-, Pd(CN)42-, Co(CN)63-, and Fe(CN)63-. Valuable metals (Pt(II) and Pd(II)) can be effectively recovered from the simulated wastewater containing four-component cyanide complexes via the two-step elution process. The recovery efficiency of Pt(II) and Pd(II) was higher than 90.0% after three adsorption-desorption cycles. The adsorption mechanism, which proceeded via ionic association (ion-exchange) and complied with the minimum surface charge density experiential principle, was confirmed using density functional theory. This study provides ideas for developing efficient and stable MORs to enable the simultaneous removal of multiple metal-cyanide complexes and recovery of valuable metals.

Epitaxial Growth of Diamond-Shaped Au1/2Ag1/2CN Nanocrystals on Graphene.

Epitaxial synthesis of inorganic nanomaterials on pristine 2D materials is of interest in the development of nanostructured devices and nanocomposite materials, but is quite difficult because pristine surfaces of 2D materials are chemically inert. Previous studies found a few exceptions including AuCN, AgCN, CuCN, and Cu0.5Au0.5CN, which can be preferentially synthesized and epitaxially aligned onto various 2D materials. Here, we discover that Au1/2Ag1/2CN forms diamond-shaped nanocrystals epitaxially grown on pristine graphene surfaces. The nanocrystals synthesized by a simple drop-casting method are crystallographically aligned to lattice structures of the underlying graphene. Our experimental investigations on 3D structures and the synthesis conditions of the nanocrystals imply that the rhombic 2D geometries originate from different growth rates depending on orientations along and perpendicular to 1D molecular chains of Au1/2Ag1/2CN. We also perform in situ TEM observations showing that Au1/2Ag1/2CN nanocrystals are decomposed to Au and Ag alloy nanocrystals under electron beam irradiation. Our experimental results provide an additional example of 1D cyanide chain families that form ordered nanocrystals epitaxially aligned on 2D materials, and reveal basic physical characteristics of this rarely investigated nanomaterial.

Reveal a hidden highly toxic substance in biochar to support its effective elimination strategy.

With the aim to develop optimized biochar with minimal contaminants, it is important significance to broaden the understanding of biochar. Here, we disclose for the first time, a highly toxic substance (metal cyanide, MCN, such as KCN or NaCN) in biochar. The cyanide ion (CN-) content in biochar can be up to 85,870 mg/kg, which is determined by the inherent metal content and type in the biomass with K and Na increasing and Ca, Mg and Fe decreasing its formation. Density functional theory (DFT) analysis shows that unstable alkali oxygen-containing metal salts such as K2CO3 can induce an N rearrangement reaction to produce for example, KOCN. The strong reducing character of the carbon matrix further converts KOCN to KCN, thus resulting biochar with high risk. However, the stable Mg, Ca and Fe salts in biomass cannot induce an N rearrangement reaction due to their high binding energies. We therefore propose that high valent metal chloride salts such as FeCl3 and MgCl2 could be used to inhibit the production of cyanide via metal interactive reaction. These findings open a new point of view on the potential risk of biochar and provide a mitigation solution for biochar's sustainable application.

Promoting sun light-induced photocatalytic degradation of toxic phenols by efficient and stable double metal cyanide nanocubes.

Aromatic substituted phenols and their by-products discharged from numerous industries are of environmental concern due to their toxic, carcinogenic, recalcitrant, and bioaccumulating properties. Therefore, their complete removal from waters by low-cost, efficient, environmentally friendly nanomaterial-based treatment techniques is desirable. Double metal cyanide complexes (DMCC) are the extremely useful heterogeneous and recoverable catalyst. Hence, green route has been developed for several DMCC and their photocatalytic efficiency was evaluated for degradation of toxic phenols. Herein, nanocubes for hexacyanocobaltate of iron (FeHCC ~ 200 nm), nickel (NiHCC < 10 nm), and zinc (ZnHCC ~ 500 nm) were synthesized after employing Aegle marmelos. Subsequently, at neutral pH and sunlight irradiation, 15 mg of catalysts were able to degrade the maximum extent of phenols (1 × 10-4 M) in the order: 3-aminophenol (96% ZnHCC > 94% FeHCC > 93% NiHCC) > phenol (94% ZnHCC > 92% FeHCC > 91% NiHCC) > 2,4-DNP (92% ZnHCC > 91% FeHCC > 90% NiHCC). This is attributed to highest basicity of 3-aminophenol containing excess of free electrons. Highest catalytic potential of ZnHCC (Xm = 0.54-0.43 mg/g) is because of its highest surface area and negative zeta potential along with sharp morphology and crystallinity. Adsorption of phenols over catalyst was statistically significant with Langmuir isotherms (R2 ≥ 0.96; p value ≤ 0.05). Small and non-toxic by-products like oxalic acid, benzoquinone, (Z)-hex-3-enedioic acid, (Z)-but-2-enal, and (Z)-4-oxobut-2-enoic acid were identified in GC-MS. Degradation modes involving hydroxylation, oxidative skeletal rearrangement, and ring opening clearly supported enhanced oxidation of phenols by •OH. Overall, due to greater active sites, high surface activity, low band gap, and semiconducting nature, DMCC revealed promising potential for solar photocatalytic remediation of wastewater.

Synthesis of vegetable-oil based polymer by terpolymerization of epoxidized soybean oil, propylene oxide and carbon dioxide.

Although carbon dioxide (CO2) is well known as one of the major green-house gases, it is also an economical C1 resource. Thus, CO2 has been regarded as an appealing starting material for the synthesis of polymers, like polycarbonates by the reaction with epoxides. Herein the reaction between natural epoxidized soybean oil (ESO), propylene oxide (PO) and CO2 under high pressure (4.0MPa) with the presence of Co-Zn double metal cyanide (Co-Zn DMC) catalyst was studied. Temperature and reaction time were varied accordingly and the products obtained were characterized by FTIR, GPC and 1H NMR. The results obtained indicate the formation of polycarbonates in the samples collected with yields vary from 60 to 85%. The number average molecular weight (Mn) of the resultant polymer prepared at reaction temperature of 80°C and reaction time of 6h can reach up to 6498g/mol.

Development of a mixed microbial culture for thiocyanate and metal cyanide degradation.

The degradation capacity of a mixed culture of Agrobacterium tumefaciens SUTS 1 and Pseudomonas monteilii SUTS 2 for thiocyanate and metal cyanide, in the form of zinc and cadmium, has been determined. The growth of a mixed culture of SUTS 1 and SUTS 2 in cyanide complexes and the cyanide removal efficiency of a fixed-film bio-column system were studied. The results showed that the mixed culture of bacteria can survive and grow in broth media containing thiocyanate and metal cyanide complexes with a maximum cell of 1.03 × 108 CFU/mL on day 3. In addition, the optimal conditions of the fixed-film bio-column system were continuously tested for 24 h, and it was found that this system had the highest removal efficiency at a flow rate of 10 mL/min and 21 min of empty bed retention time, with decreasing thiocyanate, zinc, and cadmium from 85, 0.44, and 0.044 to 65, 0.21, and 0.038 mg/L, respectively; this is in contrast to cyanide, which was not found within 12 h. Next, the conditions were maintained for 30 days, and it was found that the system had removed more than 50% of cyanide complexes, except cadmium. The complex residues were 29.96, 0.16, 0.204, and 0.085 mg/L of thiocyanate, cyanide, zinc, and cadmium, respectively. In addition, the growth of the SUTS 1 and SUTS 2 mixed culture increased. The by-product compounds sulfate and nitrate were found throughout the experiment, whereas bicarbonate and ammonia were found only on certain days.

Tolerance to silver of an Aspergillus fumigatus strain able to grow on cyanide containing wastes.

We studied the strategy of an Aspergillus fumigatus strain able to grow on metal cyanide wastes to cope with silver. The tolerance test revealed that the Minimum Inhibitory Concentration of Ag(I) was 6mM. In 1mM AgNO3 aqueous solution the fungus was able to reduce and sequestrate silver into the cell in the form of nanoparticles as evidenced by the change in color of the biomass and Electron Microscopy observations. Extracellular silver nanoparticle production also occurred in the filtrate solution after previous incubation of the fungus in sterile, double-distilled water for 72h, therefore evidencing that culture conditions may influence nanoparticle formation. The nanoparticles were characterized by UV-vis spectrometry, X-ray diffraction and Energy Dispersion X-ray analysis. Atomic absorption spectrometry revealed that the optimum culture conditions for silver absorption were at pH 8.5.The research is part of a polyphasic study concerning the behavior of the fungal strain in presence of metal cyanides; the results provide better understanding for further research targeted at a rationale use of the microorganism in bioremediation plans, also in view of possible metal recovery. Studies will be performed to verify if the fungus maintains its ability to produce nanoparticles using KAg(CN)2.