Cd Sites Research Articles

Ag Atom Induces Microstrain Environment around Cd Sites to Construct Diatomic Sites for Almost 100% CO2-to-CO Electroreduction.

Deeply understanding how local microstrain environment around diatomic sites influences their electronic state and adsorption is crucial for improving electrochemical CO2 reduction (eCO2R) reaction; however, precise engineering of the atomic microstrain environment is challenging. Herein, we fabricate Ag-CdTMT electrocatalysts with AgN2S2-CdN2S2 diatomic sites by anchoring Ag to the nodes of CdTMT (TMT = 2,4,6-trimercaptotriazine anion) coordination polymers. The Ag-CdTMT catalysts achieve approximately 100% Faradaic efficiency for CO reduction with an industrial level current density (∼200 mA cm-2 in H-cell). The embedded Ag atoms induce the formation of Ag-Cd diatomic sites with local microstrain, stretching Cd-N/S bonds, and reinforcing electron localization at Cd sites. The microstrain engineering and adjacent Ag atoms synergistically reduced Cd 4d-C 2p antibonding orbital occupancy for intensifying *COOH adsorption as the rate-determining step. This study provides novel insights into customizing the electronic structure of diatomic sites through strain engineering.

Functional investigation of a putative calcium-binding site involved in the inhibition of inositol 1,4,5-trisphosphate receptor activity.

A wide variety of factors influence inositol 1,4,5-trisphosphate (IP 3 ) receptor (IP 3 R) activity resulting in modulation of intracellular Ca 2+ release. This regulation is thought to define the spatio-temporal patterns of Ca 2+ signals necessary for the appropriate activation of downstream effectors. The binding of both IP 3 and Ca 2+ are obligatory for IP 3 R channel opening, however, Ca 2+ regulates IP 3 R activity in a biphasic manner. Mutational studies have revealed that Ca 2+ binding to a high-affinity pocket formed by the ARM3 domain and linker domain promotes IP 3 R channel opening without altering the Ca 2+ dependency for channel inactivation. These data suggest a distinct low-affinity Ca 2+ binding site is responsible for the reduction in IP 3 R activity at higher [Ca 2+ ]. We determined the consequences of mutating a cluster of acidic residues in the ARM2 and central linker domain reported to coordinate Ca 2+ in cryo-EM structures of the IP 3 R type 3. This site is termed the "CD Ca 2+ binding site" and is well-conserved in all IP 3 R sub-types. We show that the CD site Ca 2+ binding mutants where the negatively charged glutamic acid residues are mutated to alanine exhibited enhanced sensitivity to IP 3 -generating agonists. Ca 2+ binding mutants displayed spontaneous elemental Ca 2+ events (Ca 2+ puffs) and the number of IP 3 -induced Ca 2+ puffs was significantly augmented in cells stably expressing Ca 2+ binding site mutants. When measured with "on-nucleus" patch clamp, the inhibitory effect of high [Ca 2+ ] on single channel-open probability (P o ) was reduced in mutant channels and this effect was dependent on [ATP]. These results indicate that Ca 2+ binding to the putative CD Ca 2+ inhibitory site facilitates the reduction in IP 3 R channel activation when cytosolic [ATP] is reduced and suggest that at higher [ATP], additional Ca 2+ binding motifs may contribute to the biphasic regulation of IP 3 -induced Ca 2+ release.

Observing Metallic Carriers in Highly Faceted Plasmonic Cd2SnO4 Inverse Spinel Nanocrystals

AbstractCorrelating data from optical, structural, and theoretical methods allows the properties of highly faceted Cd2SnO4 (CTO) inverted spinel plasmonic semiconductor nanocrystals (PSNCs) to be fully evaluated. The use of Sn(II) in the colloidal reaction for CTO results in reproducible octahedral PSNCs with an aspect ratio of 1.30. Correlating extinction spectra with magnetic circular dichroism yields a carrier density (n = 5.19 × 1019 cm−3) and carrier effective mass (m* = 0.022me) respectively. 113Cd and 119Sn solid‐state NMR experiments show clear evidence of metallic‐like carriers in CTO NCs based upon the observation of Knight shifts. These data suggest that carrier formation in CTO arises from Sn antisite occupation of octahedral Cd sites (SnCd). From a broader perspective, the results point to wide‐bandgap spinels as being an important but understudied class of plasmonic PSNCs.

Investigating the structural, electronic, and magnetic properties of Cd1-xVxTe: Insights from First-Principles calculations

In our study, we aim to investigate the structural, electronic, and magnetic properties of CdVTe, a diluted magnetic semiconductor with a Cadmium telluride (CdTe) structure. To achieve this, we employ the full potential linear augmented plane wave method implemented in the CASTEP code, which allows us to accurately simulate the behavior of the system. To describe the electronic exchange and correlation effects, we adopt the generalized gradient approximation (GGA) within the density functional theory (DFT) framework. This choice of methodology ensures reliable and accurate calculations of the electronic and magnetic properties of Cd1-xVxTe. Our results reveal that the substitution of Vanadium (V) into the Cadmium (Cd) site of the CdTe lattice does not alter the zinc blende crystal structure, demonstrating the stability and structural integrity of the system. Furthermore, our calculations demonstrate that the introduction of Vanadium impurities leads to spin polarization within the material, resulting in the emergence of a magnetic moment. Notably, we find that a Vanadium concentration of approximately x≈0.12 exhibits the strongest magnetic properties, characterized by a significant magnetic moment. These findings provide valuable insights into the behavior and potential applications of CdVTe as a diluted magnetic semiconductor, shedding light on the interplay between structural, electronic, and magnetic properties in this material.

First-principles calculations to investigate electronic, magnetic, and optical properties at (110) and (111) surfaces of Ni adsorption on CdO

In this study, we utilised the GGA+U method via the WIEN2k software to investigate the structural, magnetic, and optoelectronic responses of two distinct surfaces, (111) and (110), to Ni adsorption on CdO at the Cd site. The analysis revealed that Ni/CdO (111) demonstrates properties akin to a semimetal or a zero-gap semiconductor across both spin orientations, while Ni/CdO (110) exhibits a metallic nature under similar conditions. These phenomena are predominantly ascribed to the orbital contributions from Ni-d, Cd-d, and O-p for the Ni/CdO (111), and Ni-d, Cd-d, and O-s for the Ni/CdO (110), respectively. A notable blue shift in the optical absorption spectra was observed for both materials. Utilising the Dielectric function, we calculated the dispersion of energy bands along with essential optical properties, including the absorption coefficient, energy loss function, and reflectivity, refractive index, and extinction coefficient. Magnetisation values for Ni/CdO (110) and Ni/CdO (111) were recorded at (−0.11794) µB and (2.17926) µB, respectively, influenced by the absorption spectrum's blue shift. Additionally, transport properties were evaluated using the BoltzTraP software over a temperature range of 0 to 800 K. Our findings suggest that Ni/CdO (110) and Ni/CdO (111) are significant for applications in spintronics and energy devices.

Heavy Metal Accumulation in Three Varieties of Mustard Grown under Five Soil Management Practices

Heavy metal pollution represents a global health issue. Different methods and technologies are adopted to mitigate the problem of heavy metal pollution. Phytoremediation has been gaining attention as an environmentally friendly method to remediate this problem. The purpose of this research is to explore the effectiveness of phytoremediation in agricultural settings to assess the effect of five soil management practices (chicken manure, sewage sludge, leaf compost, cow manure, and vermicompost) on Cd, Cu, Mo, Ni, Pb, and Zn accumulation in the mustard (leaves and pods) of three mustard Brassica juncea varieties (black mustard, yellow mustard, and mighty mustard). The accumulation in mustard was quantified using the Inductively Coupled Plasma Optical Emission Spectrometer (ICP-OES). The results showed that the bioaccumulation factor (BAF) of the three mustard varieties exceeded one (BAF > 1) for Cd and Mo. It indicates that mustard is a good accumulator of Cd and Mo, whereas BAF values for Cu, Pb, Ni, and Zn were less than one (BAF < 1). The accumulated Cu, Mo, Ni, and Zn levels were below the allowable limit, whereas the Cd and Pb levels were beyond the limit. This result indicates that the investigated mustard varieties can be grown on heavy metal polluted sites for Cd and Mo phytoremediation purposes, but care is needed with regard to Cd and Mo toxicity.

Eu Doping in the GdCd7.88 Quasicrystal and Its Approximant Crystal GdCd6.

The effect of Eu doping in the Tsai quasicrystal (QC) GdCd7.88 and its periodic 1/1 approximant crystal (AC) GdCd6 are investigated. This represents the first synthesis of Eu-containing stable QC samples, where three samples with the final composition Gd1-xEuxCd7.6±α at Eu doping concentrations x = 0.06, 0.13, and 0.19 are obtained (α ∼ 0.2). They are compared to two 1/1 ACs with compositions Gd1-xEuxCd6 (x = 0.12, 0.16). In addition, a new type of 1/1 AC, differing only by the inclusion of extra Cd sites unique to the Eu4Cd25 1/1 AC, has been discovered and synthesized for the concentrations Gd1-xEuxCd6+δ (x = 0.25, 0.33, 0.45, 0.69, 0.73, and 0 < δ ≤ 0.085). Due to the preferred cube morphology of its single grains, we refer to them as c-type 1/1 ACs and to the conventional standard ones as s-type. In both QCs and s-type ACs, the Eu content appears to saturate at a concentration of ∼20%. On the other hand, any Gd| Eu ratio is allowed in the c-type ACs, varying continuously between GdCd6 and Eu4Cd25. We describe and contrast the changes in composition, atomic structure, specific heat, and magnetic properties induced by Eu doping in the quasicrystalline phase and the s-type and c-type 1/1 ACs. By comparing our results to the literature data, we propose that the occupancy of the extra Cd sites can be used to predict the stability of Tsai-type quasicrystalline phases.

Full carbon upcycling of organophosphorus wastewater enabled by interface photolysis

The key of wastewater treatment is to reduce the toxicity of organic pollutants and ideally undergo mineralization, typically accompanying the formation of greenhouse gas CO2 in large amounts. Here, a full carbon upcycling strategy for efficient valorization of organic phosphorus (OPs) contaminants enabled by interface photolysis was developed, in which the van der Waals interface effect based on the interfacial heterojunction interaction could efficiently regulate the electron density of the UCN/CdS NPs photocatalyst interface to benefit the construction of the interface-orienteering electron pump and edge active sites. The synergistic catalysis of ·OH on the C sites and holes on the Cd sites at the photocatalyst interface edge could realize the complete photodegradation of glyphosate wastewater in 2 h to exclusively afford gas fuel CO (4124 μmol g−1) and glycine (86 %), which was likewise applicable to an extensive scope of OPs for nigh quantitative carbon upcycling. Quantum calculations elaborated that the Cd edge sites with the ability to enrich holes induced by the van der Waals interface effect could reduce the activation energy of CP bond cleavage of glyphosate activated by ·OH, resulting in CP bond scission selectivity of ca. 91.5 %, which is vital to full carbon upcycling. The oriented interface engineering offers a more eco-friendly photocatalytic protocol to facilitate both wastewater treatment and carbon resource recovery.

Study on the affinity sites of cadmium's binding to ligands by thermodynamics and nuclear magnetic resonance spectroscopy.

The affinity sites of cadmium (Cd(II)) when binding to cysteine (Cys) and glutathione (GSH) were studied via thermodynamics and nuclear magnetic resonance (NMR) spectroscopy methods. The results showed that the Cd(II) binding sites of Cys and GSH were -SH (exothermic), -NH2 (endothermic) and -COOH (endothermic). The thermodynamic behaviour of Cd(II) binding to Cys/GSH in boric acid and HEPES buffers differed, with the former being mainly endothermic and the latter mainly exothermic. It could be inferred that, in the boric acid system, the main binding site of Cd(II) with Cys and GSH is changed from -SH in HEPES to -COOH and -NH2 in boric acid. This was confirmed by the results of NMR experiments of Cd(II) with Cys/GSH. 1D 1H-NMR experiments showed that, after the combination of Cd(II) and Cys, the changes in the chemical shifts and peak strengths of protons near the -SH group for the reaction in HEPES were greater than when boric acid buffer was used. Changes in the chemical shift and peak strength of the -NH2 protons due to the binding of Cd(II) to GSH were evident in the boric acid buffer but not in HEPES. The screening of functional monomers is very important in the process of preparation of cadmium ion-imprinted materials. This research provides important theoretical and experimental guidance for the screening of functional monomers.

Relativistic DFT Calculations of Cadmium and Selenium Solid-State NMR Spectra of CdSe Nanocrystal Surfaces.

Solid-state NMR spectra have been used to probe the structure of CdSe nanocrystals and propose detailed models of their surface structures. Density functional theory (DFT)-optimized cluster models that represent probable molecular structures of carboxylate-coordinated surface sites have been proposed. However, to the best of our knowledge, 113Cd and 77Se chemical shifts have not been calculated for these surface models. We performed relativistic DFT calculations of cadmium and selenium magnetic shielding tensors on model compounds with previously measured solid-state NMR spectra with (i) the four-component Dirac-Kohn-Sham (DKS) Hamiltonian and (ii) the scalar and (iii) spin-orbit levels within the ZORA Hamiltonian. Molecular clusters with Cd and Se sites in varying bonding environments were used to model CdSe (100) and CdSe(111) surfaces capped with carboxylic acid ligands. Our calculations identify the observed 113Cd isotropic chemical shifts δ(iso) of -465, -318, and -146 ppm arising from CdSeO3, CdSe2O2, and CdSe3O surface groups, respectively, with very good agreement with experimental measurements. The 113Cd chemical shifts linearly decrease with the number of O-neighbors. The calculated spans (δ11 - δ33) encompass the experimental values for CdSe3O and CdSe2O2 clusters but are slightly larger than the measured value for CdSeO3 clusters. Relativistic DFT calculations predicted a one-bond 113Cd-77Se scalar coupling of 258 Hz, which is in good agreement with the experimental values of 250 Hz. With a dense coverage of carboxylic acid ligands, the CdSe (100) surface shows a distribution of Cd-Se bond lengths and J-couplings. Relativistic DFT simulations thus aid in interpretation of NMR spectra of CdSe nanocrystals and related nanomaterials.

Flower-like imide covalent organic framework as an electrochemical platform catcher for simultaneous sensitive detection of trace Pb(II) and Cd(II)

Heavy metal pollution in aquatic environment poses an enormous risk to ecosystems and human health. In this study, a flowerlike covalent organic framework (TpTa-COF) was synthesized by one-step solvothermal method with 2,4,6-triformylphloroglucinol (Tp) and 4, 4-diamino-tribiphenyl (Ta) as building elements. Then it was used as an effective trap to establish an electrochemical sensing platform for simultaneously sensitive detection of trace Pb(II) and Cd(II) in water. This three-dimensional flower-shaped structure exhibited exceptional adsorption capacity, large surface area, high stability, and all of which enhanced the detection sensitivity of the sensor and facilitated full contact between ions and substrate. The high oxygen content in the structure provided abundant active sites for Pb(II) and Cd(II), further enhancing its electrochemical response. The constructed sensor exhibited a linear response to Pb(II) within the concentration range of 3–60 µg/L under the optimal conditions, with a detection limit of 0.16 µg/L. Similarly, a linear response was observed for Cd(II) in the concentration range of 5–60 µg/L, with a detection limit of 0.29 µg/L. Low detection limits, excellent sensitivity, and strong stability were all features of the suggested approach. It has been successfully employed in determining Pb(II) and Cd(II) concentrations in two actual water samples. XPS, SEM-EDS mapping, and density functional theory calculations confirmed that TpTa-COF interacted with metal ions mainly via coordination with carbonyl oxygen atoms in the structure. Overall, these findings will broaden the applications of COF in the field of chemical analysis.

Improving the ability of straw biochar to remediate Cd contaminated soil: KOH enhanced the modification of K3PO4 and urea on biochar

In recent years, the improvement of soil cadmium (Cd) contamination remediation effect of biochar by modification has received wide attention. However, the effect of combined modification on biochar performance in soil Cd contamination remediation and the mechanism are still unclear. In this study, cotton straw biochar and maize straw biochar were co-modified by KOH (0, 3, 5 mol L-1), K3PO4, and urea. Then, two modified biochars with high Cd adsorption capacity were selected to test the soil Cd contamination remediation effect through a pot experiment. The results showed that the combined modification by using KOH, K3PO4, and urea significantly increased the specific surface area and nitrogen (N) and phosphorus (P) contents of biochar, providing more adsorption sites for Cd. Among the modified biochar, the cotton straw biochar modified with KOH (3 mol L-1), K3PO4, and urea (m3-CSB) had the highest adsorption capacity (111.25 mg g-1), which was 7.86 times that of cotton straw biochar (CSB). The m3-CSB for adsorption isotherm and kinetics of Cd conformed to the Langmuir model and Pseudo-second-order kinetic equation, respectively. In the pot experiment, under different exogenous Cd levels (0 (Cd0), 4 (Cd4), and 8 (Cd8) mg kg-1), m3-CSB treatment decreased soil available Cd content the most (51.68%–63.4%) compared with other biochar treatments. Besides, m3-CSB treatment significantly promoted the transformation of acid-soluble Cd to reducible, oxidizable, and residual Cd, reducing the bioavailability of Cd. At the Cd4 level, the application of m3-CSB significantly reduced cotton Cd uptake compared to CK, and the maximum reduction of Cd content in cotton fibers was as high as 81.95%. Therefore, cotton straw biochar modified with KOH (3 mol L-1), K3PO4, and urea has great potential in the remediation of soil Cd contamination.

NaCl-mediated strategies for the trade-off between Cd bioconcentration and translocation in Solanum nigrum L

Salt interference significantly affects the behavior of heavy metals in the environment. This study compared and analyzed the response process, migration, and transformation of cadmium (Cd) in the hyperaccumulator Solanum nigrum (S. nigrum) under different NaCl levels to reveal the interference mechanisms of salt in plant remediation of Cd-contaminated soil. The results showed that Cd and salt stress significantly inhibited the growth of plants. The stress effect had more potent growth inhibition at the root than aboveground, thus inducing changes in the spatial configuration of the plants (decreased root-to-aboveground biomass ratio). Salt could activate Cd in plants, enhancing the inhibitory effect on plant growth. Salt increased Cd bioavailability due to the rhizosphere acidification effect, increasing plants’ Cd accumulation. The Cd bioconcentration factor in plant roots peaked during the high Cd-high salt treatment (117.10), but the Cd accumulation of plants peaked during the high Cd-low salt treatment (233.04 μg plant−1). Salt additions and increased Cd concentrations enhanced root compartmentalization, inhibiting Cd transport to the aboveground. Changes in Fourier-transform infrared spectroscopy (FTIR) measurements confirmed that the functional groups in plants provided binding sites for Cd. These findings can help guide the phytoremediation of Cd contamination under saline soil conditions.

Ferromagnetism of Ni and I co-doped CdS: A first-principles study

This study provides insight into understanding the electronic and magnetic properties of Ni-doped and (Ni, I) co-doped CdS, which are systematically investigated by adopting the first principles approach. The findings reveal that Ni doping at the Cd site in CdS crystal modifies its ground state of non-magnetic to half-metallic ferromagnet, whereas the introduction of I as a co-doping at the S site changes the ground state of Ni-doped CdS system from half-metallic to magnetic metal. More importantly, it is found that the magnetic moment of Ni-dopant is reduced and the magnetic exchange coupling between Ni sites is enhanced after I co-doping. The estimated Curie temperature of (Ni, I) co-doped CdS is above room temperature. These findings highlight that the co-doped (Ni, I) CdS sample is a promising potential candidate for spintronics applications in future.

Enhancement of catalytic activity for hydrogenation of nitroaromatic by anionic metal-organic framework

Nitroaromatic hydrogenation catalysis without precious metals remains a longstanding challenge. The rate of electron transfer is the crucial factor affecting hydrogenation catalysis. Herein, an ionic Cd-based metal-organic framework (I-Cd-MOF) exhibiting a unique structure with one-dimensional (1D) opening nanochannels and good electron transfer ability was synthesized for catalyzing hydrogenation of 4-nitrophenol (4-NP). The catalytic activity of the unique I-Cd-MOF without noble metals is detected, which is higher than most reported noble metal catalysts. Remarkably, the reaction rate of I-Cd-MOF (4.28 min−1) is about 47.6 times higher than that of the Cd-based neutral MOF (N-Cd-MOF) with the similar crystalline structure. Liquid chromatograph mass spectrometer (LC-MS) and theoretical results demonstrate that 4-NP and five intermediates are stabilized in the channels of I-Cd-MOF, which increases the possibility of contact with H* and H2 generated at the Cd sites. The I-Cd-MOF was extended to other nitroaromatic hydrogenation catalysis, which still displays excellent activity. More importantly, the I-MOF@Filter membrane was successfully constructed for continuous hydrogenation catalytic reactions, which maintains a high catalytic performance after 7 cycles of recycling without washing. This work fills in the application of the I-MOFs in hydrogenation catalytic reactions and provides an effective way for the rapid and green degradation of nitroaromatic compounds.

Essential role of the CD docking motif of MPK4 in plant immunity, growth, and development.

MAPKs are universal eukaryotic signaling factors whose functioning is assumed to depend on the recognition of a common docking motif (CD) by its activators, substrates, and inactivators. We studied the role of the CD domain of Arabidopsis MPK4 by performing interaction studies and determining the ligand-bound MPK4 crystal structure. We revealed that the CD domain of MPK4 is essential for interaction and activation by its upstream MAPKKs MKK1, MKK2, and MKK6. Cys181 in the CD site of MPK4 was shown to become sulfenylated in response to reactive oxygen species invitro. To test the function of C181 invivo, we generated wild-type (WT) MPK4-C181, nonsulfenylatable MPK4-C181S, and potentially sulfenylation mimicking MPK4-C181D lines in the mpk4 knockout background. We analyzed the phenotypes in growth, development, and stress responses, revealing that MPK4-C181S has WT activity and complements the mpk4 phenotype. By contrast, MPK4-C181D cannot be activated by upstream MAPKK and cannot complement the phenotypes of mpk4. Our findings show that the CD motif is essential and is required for activation by upstream MAPKK for MPK4 function. Furthermore, growth, development, or immunity functions require upstream activation of the MPK4 protein kinase.

Enhanced the Efficiency of Electrocatalytic CO2 -to-CO Conversion by Cd Species Anchored into Metal-Organic Framework.

Metal-organic frameworks (MOFs) as a promising platform for electrocatalytic CO2 conversion are still restricted by the low efficiency or unsatisfied selectivity for desired products. Herein, zirconium-based porphyrinic MOF hollow nanotubes with Cd sites (Cd-PCN-222HTs) are reported for electrocatalytic CO2 -to-CO conversion. The dispersed Cd species are anchored in PCN-222HTs and coordinated by N atoms of porphyrin structures. It is discovered that Cd-PCN-222HTs have glorious electrocatalytic activity for selective CO production in ionic liquid-water (H2 O)-acetonitrile (MeCN) electrolyte. The CO Faradaic efficiency (FECO ) of >80% could be maintained in a wide potential range from -2.0 to -2.4V versus Ag/Ag+ , and the maximum current density could reach 68.0mA cm-2 at -2.4V versus Ag/Ag+ with a satisfied turnover frequency of 26220 h-1 . The enhanced efficiency of electrocatalytic CO2 conversion of Cd-PCN-222HTs is closely related to its hollow structure, anchored Cd species, and good synergistic effect with electrolyte. The density functional theory calculations indicate that the dispersed Cd sites anchored in PCN-222HTs not only favor the formation of *COOH intermediate but also hinder the hydrogen evolution reaction, resulting in high activity of electrocatalytic CO2 -to-CO conversion.

Direct Observation of Group-V Dopant Substitutional Defects in CdTe Single Crystals.

Point defect chemistry strongly affects the fundamental properties of materials and has a decisive impact on device performance. The Group-V dopant is prominent acceptor species with high hole concentration in CdTe; however, its local atomic structure is still not clear owing to difficulties in definitive measurements and discrepancies between experimental observations and theoretical models. Herein, we report on direct observation of the local structure for the As dopant in CdTe single crystals by the X-ray fluorescence holography (XFH) technique, which is a powerful tool to visualize three-dimensional atomic configurations around a specific element. The XFH result shows the As substituting on both Cd (AsCd) and Te (AsTe) sites. Although AsTe has been well known as a shallow acceptor, AsCd has not attracted much attention and been discussed so far. Our results provide new insights into point defects by expanding the experimental XFH study in combination with theoretical first-principles studies in II-VI semiconductors.

NaHCO3 activated sludge-derived biochar by KMnO4 modification for Cd(II) removal from aqueous solutions.

The surface flat pristine biochar provides limited adsorption sites for Cd(II) adsorption. To address this issue, a novel sludge-derived biochar (MNBC) was prepared by NaHCO3 activation and KMnO4 modification. The batch adsorption experiments illustrated that the maximum adsorption capacity of MNBC was twice that of pristine biochar and reached equilibrium more quickly. The pseudo-second order and Langmuir model were more suitable for analyzing the Cd(II) adsorption process on MNBC. Na+, K+, Mg2+, Ca2+, Cl- and NO-3 had no effect on the Cd(II) removal. Cu2+ and Pb2+ inhibited the Cd(II) removal, while PO3-4 and humic acid (HA) promoted it. After 5 repeated experiments, the Cd(II) removal efficiency on MNBC was 90.24%. The Cd(II) removal efficiency of MNBC in different actual water bodies was over 98%. Furthermore, MNBC owned excellent Cd(II) adsorption performance in fixed bed experiments, and the effective treatment capacity was 450 BV. The co-precipitation, complexation, ion exchange and Cd(II)-π interaction were involved in Cd(II) removal mechanism. XPS analysis showed that NaHCO3 activation and KMnO4 modification enhanced the complexation ability of MNBC to Cd(II). The results suggested that MNBC can be used as an effective adsorbent for treating of Cd-contaminated wastewater.

Single‐Atom Cadmium‐N4 Sites for Rechargeable Li–CO2 Batteries with High Capacity and Ultra‐Long Lifetime

AbstractThe rechargeable Li–CO2 battery shows great potential in civil, military, and aerospace fields due to its high theoretical energy density and CO2 capture capability. To facilitate the practical application of Li–CO2 battery, the design of efficient, low‐cost, and robust non‐noble metal cathodes to boost CO2 reduction/evolution kinetics is highly desirable yet remains a challenge. Herein, single‐atom cadmium is reported with a Cd‐N4 coordination structure enable rapid kinetics of both the discharge and recharge process when employed as a cathode catalyst, and thus facilitates exceptional rate performance in a Li–CO2 battery, even up to 10 A g−1, and remains stable at a high current density (100 A g−1). An unprecedented discharge capacity of 160045 mAh g−1 is attained at 500 mA g−1. Excellent cycling stability is maintained for 1685 and 669 cycles at 1 A g−1 and capacities of 0.5 and 1 Ah g−1, respectively. Density functional theory calculations reveal low energy barriers for both Li2CO3 formation and decomposition reactions during the respective discharge and recharge process, evidencing the high catalytic activity of single Cd sites. This study provides a simple and effective avenue for developing highly active and stable single‐atom non‐precious metal cathode catalysts for advanced Li–CO2 batteries.