Zn CO Research Articles

Ascertaining sensitive exposure biomarkers of various metal(loid)s to embryo implantation

Close relationships exist between metal(loid)s exposure and embryo implantation failure (EIF) from animal and epidemiological studies. However, there are still inconsistent results and lacking of sensitive metal(loid) exposure biomarkers associated with EIF risk. We aimed to ascertain sensitive metal(loid) biomarkers to EIF and provide potential biological explanations. Candidate metal(loid) biomarkers were measured in the female hair (FH), female serum (FS), and follicular fluid (FF) with various exposure time periods. An analytical framework was established by integrating epidemiological association results, comprehensive literature searching, and knowledge-based adverse outcome pathway (AOP) networks. The sensitive biomarkers of metal(loid)s along with potential biological pathways to EIF were identified in this framework. Among the concerned 272 candidates, 45 metal(loid)s biomarkers across six time periods and three biomatrix were initially identified by single-metal(loid) analyses. Two biomarkers with counterfactual results according to literature summary results were excluded, and a total of five biomarkers were further determined from 43 remained candidates in mixture models. Finally, four sensitive metal(loid) biomarkers were eventually assessed by overlapping AOP networks information, including Se and Co in FH, and Fe and Zn in FS. AOP networks also identified key GO pathways and proteins involved in regulation of oxygen species biosynthetic, cell proliferation, and inflammatory response. Partial dependence results revealed Fe in FS and Co in FH at their low levels might be potential sensitive exposure levels for EIF. Our study provided a typical framework to screen the crucial metal(loid) biomarkers and ascertain that Se and Co in FH, and Fe and Zn in FS played an important role in embryo implantation.

A bismuth-atom electrocatalyst for a stable and economical aqueous Zn–CO2 battery

A single Bi-metal atom electrocatalyst was employed in an H-type cell to produce liquid high hydrocarbon products. The customized Zn–CO2 device with Bi-SAs/NC exhibited an elevated power density of 3.8 mW cm−2.

Aqueous Zn–CO2 batteries: a route towards sustainable energy storage

This review systematically summarizes the working principles and devices, and the different types of catalytic cathodes used for Zn–CO2 batteries. The challenges and prospects in this field are also particularly discussed.

Heterogeneous Cobalt Phthalocyanine/Sulfur‐Modified Hollow Carbon Sphere for Boosting CO2 Electroreduction and Zn–CO2 Batteries

AbstractTuning coordination environment of single‐atom catalysts (SACs) is widely applied for the electrochemical CO2 reduction reaction (CO2RR). However, the influence of the interaction between SACs and support on the catalytic performance are not comprehensive. Herein, taking cobalt phthalocyanine (CoPc) as a conceptual example, a hetero S‐atom doping strategy of hollow carbon sphere (S‐NHC) is put forward as a carrier, revealing the intrinsic relationship between microenvironment regulation and catalytic activity of single Co‐atom. The additional S doping may induce more carbon defect and increases the content of pyrrolic N in the S‐NHC sample, leading to stronger electronic interaction of heterogeneous CoPc/S‐NHC for boosting CO2RR performance. Remarkably, the catalyst achieves a highest CO selectivity of nearly 100% at −0.6 V, and the FECO are over 90% in a wide potential range from −0.4 to −0.8 V in a flow cell. The maximum power density is high as 2.68 mW cm−2 at 4.7 mA cm−2 for the Zn–CO2 battery with CoPc/S‐NHC cathode. In situ attenuated total reflection infrared (ATR‐IR) spectroscopy reveals the formation of key *COOH and *CO intermediates, while the calculation result confirm the optimized Gibbs free energy of these intermediates on CoPc/S‐NHC, suggesting the feasibility of the regulation strategy.

An investigation of heavy metals concentration in rainwater and their effects on human health in Kurdistan Region, Iraq

One possible source of fresh water is rainfall. Nonetheless, the natural composition of rainwater may change due to air pollution in any areas. The Kwashe and Gara in the Duhok Governorate, in the Kurdistan region of Iraq, was selected as the study areas. Heavy metals concentration of rainwater was investigated. Seven samples were taken during rainy January and February 2023 for this investigation, and a statistical analysis was carried out to identify the factors influencing the quality of the rainwater. The concentrations of heavy metals (Zn, Pb, Ni, Cr, Cd, Mn, Cu, Fe, and Co) were measured with an atomic absorption spectrophotometer (AAS) and compared to WHO standards. The purpose of the study was to compare the heavy metal content of study area rainwater to WHO standards in order to determine the effects of these metals on community members' individual health as well as the environment. The heavy metal concentrations dropped in the following order: (Zn, Pb, Ni, Cr, Cd, Mn, Cu, Fe, and Co in Kwashe and Zn > Ni > Cu > Pb > Cr > Fe > Mn > Cd > Co in Gara). The following heavy metals are within the WHO's permissible limit: Fe, Cu, Zn, Mn, and Co; the others exceeded it. The results indicate that the rainwater sources in the study areas are unsafe and unfit for human consumption. Because of this, rainwater from research areas needs to be treated before drinking in order to prevent Pb, Cd, Ni, and Cr-related health problems.

Dual-Anion Regulation for Reversible and Energetic Aqueous Zn-CO2 Batteries.

Aqueous Zn-CO2 batteries can not only convert CO2 into high-value chemicals but also store/output electric energy for external use. However, their performance is limited by sluggish and complicated CO2 electroreduction at the cathode. Herein, a dual-anion regulated Bi electrocatalyst is developed to selectively reduce CO2 to formate with a Faradaic efficiency of up to 97% at a large current density of 250mAcm-2. With O and/or F, the rate-determine step of CO2 electroreduction has been manipulated (from the first hydrogenation to *HCOOH desorption step) with a reduced energy barrier. Significantly, the fabricated Zn-CO2 battery exhibits a high discharge voltage of 1.2V, optimal power density of 4.51mWcm-2, remarkable energy density of 802Whkg-1, and energy-conversion efficiency of 70.74%, stability up to 200 cycles and 68h. This study provides possible strategies to fabricate reversible and energetic aqueous Zn-CO2 batteries by addressing cathodic problems.

The behavior of potentially toxic elements in the technogenic soil-plant system: A study of Salicornia europaea L. from sites affected by the soda industry

Soils created or significantly transformed by human activity are called technogenic soils. They have specific morphological, physical, chemical, and biological characteristics resulting from introducing technogenic materials that are often not inert to the environment. Very little research is still conducted in technogenic or post-technogenic areas based on analyzing environmental samples (plants and soils). Experimental, model-based studies dominate and often have limited reference to actual environmental conditions. That is why this study was carried out in areas affected by waste from the soda industry referring to the living labs concept. We tested the hypothesis that the impact of highly saline industrial waste has contributed to the formation of a specific pattern of relocation and accumulation of potentially toxic elements (PTEs) in the plant-soil system. We applied halophyte Salicornia europaea as a model plant and analyzed the chemical properties of soil and plant materials collected from five study sites. Our results demonstrate that the highest bioconcentration factors for shoots or roots were observed in cadmium (Cd), copper (Cu), nickel (Ni), and zinc (Zn), with a value of more than 1. Translocation factors for all metals were less than 1 meaning more parts of PTEs were accumulated in the roots. The lowest storage factors were related to Ba, Cd, Cu, and Zn, indicating more amounts of these metals were transferred to the shoots. We revealed that S. europaea could be used for phytoremediation of soils contaminated by PTEs adopting phytostabilization for Ba, Co, Ni, and lead (Pb), and phytoextraction for Cd, Cu, and Zn. In this way, our findings can have a significant contribution to achieving one of the Sustainable Development Goals of the UN 2030 Agenda (goal no. 15), focusing, among others, on halting and reversing land and natural habitat degradation and stopping biodiversity loss.

Regulating the Electronic Structure of Bismuth Nanosheets by Titanium Doping to Boost CO2 Electroreduction and Zn–CO2 Batteries (Small 38/2023)

Regulating the Electronic Structure of Bismuth Nanosheets by Titanium Doping to Boost CO₂ Electroreduction and Zn–CO₂ Batteries (Small 38/2023)

Tuning the Metal Electronic Structure of Anchored Cobalt Phthalocyanine via Dual‐Regulator for Efficient CO2 Electroreduction and Zn–CO2 Batteries

Adv. Funct. Mater. 2022, 2110649 DOI: 10.1002/adfm.202110649 In the original published article, the label of one curve in Figure 2e and a value in Figure 4d were incorrect. One image of Figure 4b (NHCS) and one image of Figure 4e ([email protected]) were misplaced. One image in Figure S38a, one image in inset of Figure S38b, and one image in inset of Figure S38d in the Supporting Information were misplaced. In addition, the caption of Figure 3d was mislabeled. The corrected figures are as follows. The corrected caption is as follows. Figure 3d. d) Tafel slope These errors do not affect the conclusions of the report. The authors apologize for the inconvenience these errors may have caused.

Recent advances in Zn–CO2 batteries for the co-production of electricity and carbonaceous fuels

Electrochemical CO 2 reduction has been considered a promising approach to neutralizing the global CO 2 level. As an intriguing technique, metal-CO 2 battery devices can not only capture CO 2 into valuable carbonaceous chemicals and reduce the CO 2 concentration in the atmosphere but enable energy conversion. Among metal-CO 2 batteries, aqueous Zn–CO 2 batteries, especially rechargeable systems, exhibit flexible CO 2 electrochemistry in terms of multi-carbon chemicals, which are gaseous or water-soluble, in favor of rechargeability and cycling durability of aqueous battery systems. Despite the increasing number of publications on Zn–CO 2 batteries in the past three years, this field is still in its beginning stage and facing many challenges considering the capability of CO 2 fixation and battery performance. Herein, we present a timely and overall summary of the recent progress in Zn–CO 2 batteries, including fundamental mechanisms, affecting factors on electrochemical performance, catalyst cathodes, and electrolytes (catholytes and anolytes). Besides, we assess the application potential of Zn–CO 2 batteries and compare this with those of alkali metal-CO 2 batteries based on CO 2 fixation and battery performance. Finally, we point out some current challenges for the further development of Zn–CO 2 batteries and put forward perspectives of the research directions for practical applications of Zn–CO 2 batteries in the future.

Atomically Dispersed Metal‐Based Catalysts for Zn–CO2Batteries

Rechargeable aqueous Zn–CO2batteries show great promise in meeting severe environmental problems and energy crises due to their combination of CO2utilization and energy output, as well as advantages of high theoretical energy density, abundant raw materials, and high safety. Developing high‐efficiency and stable CO2reduction reaction (CO2RR) electrocatalysts is of critical importance for the promotion of this technology. Atomically dispersed metal‐based catalysts (ADMCs), with extremely high atom‐utilization efficiency, tunable coordination environments, and superior intrinsic catalytic activity, are emerging as promising candidates for Zn–CO2batteries. Herein, some recent developments in atomically dispersed metal‐based catalysts for Zn–CO2batteries are summarized, including transition metal and non‐transition metal sites. Moreover, various synthetic strategies, characterization methods, and the relationship between active site structures and CO2RR activity/Zn–CO2battery performance are introduced. Finally, some challenges and perspectives are also proposed for the future development of ADMCs in Zn–CO2batteries.

Tuning the Metal Electronic Structure of Anchored Cobalt Phthalocyanine via Dual‐Regulator for Efficient CO2 Electroreduction and Zn–CO2 Batteries

AbstractHeterogeneous macromolecule catalysts have been known as efficient electrocatalysts for CO2 reduction reaction, however, manipulating the activity of heterogeneous molecules via controllable metal electronic structure is still challenging. Herein, different CO2 activated 3D, robust, nitrogen‐doped hollow carbon spheres are synthesized to anchor cobalt phthalocyanine as molecularly dispersed electrocatalysts, where the electron‐withdrawing coeffect of carbon defects and heteroatom N is responsible for tuning the electronic structure of metal center. The optimal electrocatalyst reveals high CO faradaic efficiency (FECO) of 95.68%, turnover frequency of 13.80 s−1, and current density of 16.49 mA cm−2 at an overpotential of 760 mV. The control experiment and DFT calculations unveil that the significant activity is mainly ascribed to the optimal electron‐withdrawing coeffect of carbon defects and pyrrolic N, which reduce the electron density of Co center to facilitate CO2 activated to form *COOH intermediate on Co(I) active sites during electrocatalysis. The 2p‐charge loss of Co is summarized as an activity descriptor, which steers the current density and production rate toward CO. Furthermore, the design strategy can universally fabricate the hybrid MPc catalyst with transitional metal (Ni, Fe) site while a rechargeable Zn–CO2 battery is devised to deliver a maximal power density of 1.02 mW cm−2.

Mixed metal node effect in zeolitic imidazolate frameworks.

We synthesized two series of bimetallic (zinc and cobalt) zeolitic imidazolate frameworks (ZIF-62) under different solvothermal conditions. It is found that the structure of the derived ZIF crystals is highly sensitive to synthesis conditions. One series possesses the standard ZIF-62 structure, whereas the other has a mixed structure composed of both the standard structure and an unknown one. The standard series exhibits a slight negative deviation from linearity of melting temperature (Tm) and glass transition temperature (Tg) with the substitution of Co for Zn. In contrast, the new series displays a stronger negative deviation. These negative deviations from linearity indicate the mixed metal node effect in bimetallic ZIF-62 due to the structural mismatch between Co2+ and Zn2+ and to the difference in their electronic configurations. The new series involves both cobalt-rich and zinc-rich phases, whereas the standard one shows one homogeneous phase. Density functional theory calculations predict that the substitution of Co for Zn increases the bulk modulus of the ZIF crystals. This work indicates that the structure, melting behaviour, and mechanical properties of ZIFs can be tuned by metal node substitution and by varying the synthetic conditions. Both series of ZIFs have higher glass forming abilities due to their higher Tg/Tm ratios (0.77–0.84) compared to most good glass formers.

Synergistic effect of Cu/Cu2O surfaces and interfaces for boosting electrosynthesis of ethylene from CO2 in a Zn–CO2 battery

We constructed Cu/Cu2O hybrid catalysts with highly active surfaces/interfaces to realize a synergistic effect, thus improving the selectivity and efficiency of C2H4 production.

Bismuth with abundant defects for electrocatalytic CO2 reduction and Zn-CO2 batteries.

To regulate the electronic structure of Bi sites and enhance their intrinsic activity, metal Bi with abundant defects was constructed. The optimized sample displayed a higher selectivity (93.9% at -0.9 V) and a larger current density (-10 mA cm-2 at -1.0 V) towards electrocatalytic CO2 reduction to formate, which can be mainly attributed to abundant defect sites and the optimized electronic structure. The assembled Zn-CO2 batteries displayed a power density of 1.16 mW cm-2 and a cycling stability up to 22 h. This work deepens the research of Bi-based catalysts towards CO2 transformation and related energy devices.

Surface sulfur vacancies enhanced electron transfer over Co-ZnS quantum dots for efficient degradation of plasticizer micropollutants by peroxymonosulfate activation

Peroxymonosulfate (PMS) activation in heterogeneous processes is a promising water treatment technology. Nevertheless, the high energy consumption and low efficiency during the reaction are ineluctable, due to electron cycling rate limitation. Herein, a new strategy is proposed based on a quantum dots (QDs)/PMS system. Co-ZnS QDs are synthesized by a water phase coprecipitation method. The inequivalent lattice-doping of Co for Zn leads to the generation of surface sulfur vacancies (SVs), which modulates the surface of the catalyst to form an electronic nonequilibrium surface. Astonishingly, the plasticizer micropollutants can be completely degraded within only tens of seconds in the Co-ZnS QDs/PMS system due to this type of surface modulation. The interfacial reaction mechanism is revealed that pollutants tend to be adsorbed on the cobalt metal sites as the electron donors, where the internal electrons of pollutants are captured by the metal species and transferred to the surface SVs. Meanwhile, PMS adsorbed on the SVs is reduced to radicals by capturing electrons, achieving effective electron recovery. Dissolved oxygen (DO) molecules are also easily attracted to catalyst defects and are reduced to O 2 •− , further promoting the degradation of pollutants. A new strategy is reported to generate electron-rich/poor reaction sites on the catalyst surface by constructing sulfur vacancies through Co doping into the ZnS QDs lattice. PMS and DO are captured by sulfur vacancies and reduced to reactive oxygen species, thus rapidly degrading organic pollutants.

Asymmetric Oxo-Bridged ZnPb Bimetallic Electrocatalysis Boosting CO2 -to-HCOOH Reduction.

Electrochemical CO2 reduction (ECR) is one of the promising CO2 recycling technologies sustaining the natural carbon cycle and offering more sustainable higher‐energy chemicals. Zn‐ and Pb‐based catalysts have improved formate selectivity, but they suffer from relatively low current activities considering the competitive CO selectivity on Zn. Here, lead‐doped zinc (Zn(Pb)) electrocatalyst is optimized to efficiently reduce CO2 to formate, while CO evolution selectivity is largely controlled. Selective formate is detected with Faradaic efficiency (FEHCOOH) of ≈95% at an outstanding partial current density of 47 mA cm–2 in a conventional H‐Cell. Zn(Pb) is further investigated in an electrolyte‐fed device achieving a superior conversion rate of ≈100 mA cm–2 representing a step closer to practical electrocatalysis. The in situ analysis demonstrates that the Pb incorporation plays a crucial role in CO suppression stem from the generation of the Pb–O–C–O–Zn structure rather than the CO‐boosted Pb–O–C–Zn. Density functional theory (DFT) calculations reveal that the alloying effect tunes the adsorption energetics and consequently modifies the electronic structure of the system for an optimized asymmetric oxo‐bridged intermediate. The alloying effect between Zn and Pb controls CO selectivity and achieves a superior activity for a selective CO2‐to‐formate reduction.

Biomass-Derived N-Doped Carbon for Efficient Electrocatalytic CO2 Reduction to CO and Zn-CO2 Batteries.

Conversion of CO2 into valuable chemicals via electrochemical CO2 reduction reaction (CO2RR) is a promising technology to alleviate the energy crisis and the greenhouse effect. Herein, low-cost wood biomass was applied as the carbon source to prepare nitrogen (N)-doped carbon electrocatalysts for the conversion of CO2 to CO and further as the cathode material for Zn-CO2 batteries. By virtue of N-doping and assistance of FeCl3, a cedar biomass-derived three-dimensional (3D) N-doped graphitized carbon with a high N-doping content (5.38%), an ultrahigh specific surface area (1673.6 m2 g-1), rich nanopores, and sufficient active N sites was successfully obtained, which exhibited super CO2RR activity with a high faradaic efficiency of 91% at a low applied potential of 0.56 V (vs RHE) and a long-term stability for at least 20 h. Furthermore, a Zn-CO2 battery with it as the cathode material delivered a stable open circuit voltage of 0.79 V, a peak power density of 0.51 mW cm-2 at 2.14 mA cm-2, and a maximum faradaic efficiency to CO of 80.4% at 2.56 mA cm-2, indicating that it could be applied in a practical process by using CO2 to generate power with the production of CO. Density functional theory calculations revealed that pyridinic N could more effectively decrease the free energy barriers for CO2RR and boost the reaction. This work not only revealed a facile approach to convert waste biomass into N-doped-graphitization carbon as valuable CO2RR electrocatalysts but also provided a new strategy to achieve "carbon solving carbon's problem".

Coralloid Au enables high-performance Zn–CO2 battery and self-driven CO production

Coralloid Au is reported as an efficient and stable electrocatalyst for catalyzing membrane electrode assembly with 94.2% FECO, Zn–CO2 battery with 0.7 mW cm−2 power density and self-driven CO2 electrolysis with 0.44 ml h−1 CO productivity.

In/ZnO@C hollow nanocubes for efficient electrochemical reduction of CO2 to formate and rechargeable Zn–CO2 batteries

In/ZnO@C hollow nanocubes derived from In(OH)3-doped Zn-MOFs were developed for the electrochemical reduction of CO2 to formate and rechargeable aqueous Zn–CO2 batteries.