Promises of Main Group Metal–Based Nanostructured Materials for Electrochemical CO2 Reduction to Formate

Selective CO₂ reduction to formic acid or formate is the most technologically and economically viable approach to realize electrochemical CO₂ valorization. Main group metal–based (Sn, Bi, In, Pb, and Sb) nanostructured materials hold great promise, but are still confronted with several challenges. Here, the current status, challenges, and future opportunities of main group metal–based nanostructured materials for electrochemical CO₂ reduction to formate are reviewed. Firstly, the fundamentals of electrochemical CO₂ reduction are presented, including the technoeconomic viability of different products, possible reaction pathways, standard experimental procedure, and performance figures of merit. This is then followed by detailed discussions about different types of main group metal–based electrocatalyst materials, with an emphasis on underlying material design principles for promoting the reaction activity, selectivity, and stability. Subsequently, recent efforts on flow cells and membrane electrode assembly cells are reviewed so as to promote the current density as well as mechanistic studies using in situ characterization techniques. To conclude a short perspective is offered about the future opportunities and directions of this exciting field.     

Graphitic‐Shell Encapsulation of Metal Electrocatalysts for Oxygen Evolution,Oxygen Reduction,and Hydrogen Evolution in Alkaline Solution

Developing highly efficient, cost effective, and environmentally friendly electrocatalysts for the oxygen evolution reaction (OER), oxygen reduction reaction (ORR), and hydrogen evolution reaction (HER) is of interest for sustainable and clean energy technologies, including metal–air batteries and fuel cells. In this work, the screening of electrocatalytic activities of a series of single metallic iron, cobalt, and nickel nanoparticles and their binary and ternary alloys encapsulated in a graphitic carbon shell toward the OER, ORR, and HER in alkaline media is reported. Synthesis of these compounds proceeds by a two‐step sol–gel and carbothermal reduction procedure. Various ex situ characterizations show that with harsh electrochemical activation, the graphitic shell undergoes an electrochemical exfoliation. The modified electronic properties of the remaining graphene layers prevent their exfoliation, protect the bulk of the metallic cores, and participate in the electrocatalysis. The amount of near‐surface, higher‐oxidation‐state metals in the as‐prepared samples increases with electrochemical cycling, indicating that some metallic nanoparticles are not adequately encased within the graphite shell. Such surface oxide species provide secondary active sites for the electrocatalytic activities. The Ni–Fe binary system gives the most promising results for the OER, and the Co–Fe binary system shows the most promise for the ORR and HER.     

佛山城市典型森林群落土壤重金属分布、流通及枯落物富集特征

富集重金属的枯落物分解可能提高重金属暴露率,增加人体接触健康风险。为了解南方城市土壤重金属在森林生态系统中的分布及流转情况,通过调查研究了佛山市8个典型森林群落土壤及枯落物重金属含量,分析了各森林群落枯落物对不同重金属的富集效应及重金属随枯落物回归土壤流通量。结果表明：1）城市森林各土壤重金属含量在不同典型群落间差异显著（P<0.05）,差异最大为Pb、Cr、Zn,As、Cu、Ni次之,Hg、Cd最小;土层深度（0-20,20-40,40-60 cm）对重金属含量影响显著（P<0.05）,差异最大为Cd、Hg,其次为As、Cu,最小为Zn、Ni、Pb、Cr。整体上,Cd、Hg、As、Pb、Zn在0-20 cm最高,表层富集特征明显,Cr和Ni在40-60 cm最高。2）8个森林群落中阴香-白楸-醉香含笑群落（CMMC）枯落物对8种重金属的综合富集系数（TBCF,66.76）最高,其中以Cd的富集效果最突出,富集系数为44.45,且对Pb、Cu、Zn也相对富集;最低的为黧蒴锥-香椿-樟树群落（CTCC）,综合富集系数（TBCF）为8.09,仅对Cd、Cr、Cu相对富集,对其余重金属富集效应不明显。3）相关分析显示,群落重金属枯落物流通量与0-60 cm土壤重金属平均含量（Cr和Ni除外）无显著相关性。本研究对城市森林建设管理及筛选重金属富集植物及群落具有较强理论及实践意义。     

纳塔栎和柳叶栎对铅锌矿区污染土壤的修复潜力分析:田间试验

通过野外调查、采样和实验室分析方法,研究优新景观树种纳塔栎（Quercus nuttallii）和柳叶栎（Quercus phellos）对湖南郴州Pb、Zn矿区复合污染土壤的适应性和修复潜力。试验设计A、B、E区种植1年生纳塔栎,C、D区种植1年生柳叶栎,1年后测量株高、地径、生物量等生长指标,随机采集植物全株及根际土壤,测试植物根际土壤和树木组织中的重金属含量。试验结果：Pb、Zn矿区土壤受到重金属Cd、Pb、Zn和As的复合污染,不同区域的土壤表现出污染异质性,采用单污染指数（Pi）和内梅罗指数（P_N）评价不同地块的污染程度,A区尾矿库（P_N=20.08）和B区（P_N=3.14）为重度复合污染,C区（P_N=2.43）为中度复合污染,D区（P_N=1.55）和E区（P_N=1.07）为轻微污染。纳塔栎和柳叶栎在以上不同污染地块均能正常生长,株高、地径和生物量与复合污染指数（内梅罗指数）及重金属含量呈负相关。其中纳塔栎对Cd的生物富集系数（BCF）在A、B、E区分别为6.27-8.37、3.67-4.38、42.93-52.75,高于C、D区柳叶栎对Cd的生物富集系数1.79-2.15、0.89-1.07。B-E区Zn的转运系数（TF）在1.79-2.28之间,A区Zn的转运系数为0.43。结论：纳塔栎和柳叶栎表现出较强的重金属耐性,对Cd具有较高的生物富集能力,对Zn具有较高的转运能力。其中纳塔栎对重金属积累能力较强,可作为亚热带地区铅锌矿区Cd、Pb、Zn、As复合污染土壤的植被恢复及生态修复候选树种。     

Kinetic analysis of metal uptake by dry and gel alginate particles

The kinetics of metal uptake by gel and dry calcium alginate beads was analysed using solutions of copper or lead ions. Gel beads sorbed metal ions faster than the dry ones and larger diffusivities of metal ions were calculated for gel beads: approximately 10⁻⁴ cm²/min vs. 10⁻⁶ cm²/min for dry beads. In accordance, scanning electron microscopy and nitrogen adsorption data revealed a low porosity of dry alginate particles. However, dry beads showed higher sorption capacities and a mechanical stability more suitable for large-scale use. Two sorption models were fitted to the kinetic results: the Lagergren pseudo-first order and the Ho and McKay pseudo-second order equations. The former was found to be the most adequate to model metal uptake by dry alginate beads and kinetic constants in the orders of 10⁻³ and 10⁻² min⁻¹ were obtained for lead solutions with concentrations up to 100 g/m³. The pseudo-first order model was also found to be valid to describe biosorbent operation with a real wastewater indicating that it can be used to design processes of metal sorption with alginate-based materials.     

Effects of zinc toxicity on sugar beet (Beta vulgaris L.) plants grown in hydroponics

The effects of high Zn concentration were investigated in sugar beet ( Beta vulgaris L.) plants grown in a controlled environment in hydroponics. High concentrations of Zn sulphate in the nutrient solution (50, 100 and 300 μ m ) decreased root and shoot fresh and dry mass, and increased root/shoot ratios, when compared to control conditions (1.2 μ m Zn). Plants grown with excess Zn had inward-rolled leaf edges and a damaged and brownish root system, with short lateral roots. High Zn decreased N, Mg, K and Mn concentrations in all plant parts, whereas P and Ca concentrations increased, but only in shoots. Leaves of plants treated with 50 and 100 μ m Zn developed symptoms of Fe deficiency, including decreases in Fe, chlorophyll and carotenoid concentrations, increases in carotenoid/chlorophyll and chlorophyll a / b ratios and de-epoxidation of violaxanthin cycle pigments. Plants grown with 300 μ m Zn had decreased photosystem II efficiency and further growth decreases but did not have leaf Fe deficiency symptoms. Leaf Zn concentrations of plants grown with excess Zn were high but fairly constant (230–260 μg·g⁻¹ dry weight), whereas total Zn uptake per plant decreased markedly with high Zn supply. These data indicate that sugar beet could be a good model to investigate Zn homeostasis mechanisms in plants, but is not an efficient species for Zn phytoremediation.     

The Influence of Physical Habitat,Pyrethroids, and Metals on Benthic Community Condition in an Urban and Residential Stream in California

This study was designed to characterize benthic communities and physical habitat in both an urban (Kirker Creek) and residential (Pleasant Grove Creek) stream in California in late spring of 2006 and 2007. Concurrent water quality evaluations, physical sediment parameters, pyrethroids, bulk metals, and SEM/AVS ratios were also measured during both years of this study. The relationship of various benthic metrics to physical habitat metrics, pyrethroids, and metals was evaluated for each stream using stepwise multiple linear regressions with both years combined for each stream, as well as both years and both streams combined, to increase the statistical power for determining significant relationships. Physical habitat was determined to be poor in each stream during both years of sampling. More than 100 benthic taxa were reported annually for both streams based on 2006 and 2007 sampling. A significant result from the stepwise regression analysis combining data for 2 years across both streams is that when habitat metrics and to a lesser degree metals are considered in the statistical models pyrethroids do not display any significant relationships to the benthic metrics. In summary, it is apparent from this analysis that the health of benthic communities in both streams is primarily affected by habitat metrics.     

Human Health Risk Assessment for Environmental Exposure to Metals in the Catalan Stretch of the Ebro River,Spain

The aim of this study was to investigate the environmental impact and the human health risks associated with metals exposure in the Catalan stretch of the Ebro River, Spain. The concentrations of the following elements were determined in soils and tap water: As, Cd, Cr, Cu, Hg, Mn, Ni, and Pb. Carcinogenic and non-carcinogenic risks were separately assessed for adults and children. Relatively low metal concentrations in tap water were found. It indicates that water intake is not a relevant source of metals for human health impact in the area under evaluation. In turn, the levels of metals in soils were similar or less than those found in a number of recent worldwide surveys. The presence of industrial facilities located upstream the Ebro River, including a chloralkali plant, should not mean additional non-carcinogenic risks for the population living in the area. The results of the current study allow us to establish that the concentrations of most carcinogenic elements (with the exception of As) should not mean potential health risks for the local population. However, because of the relatively high levels of geological origin found for As, a continued monitoring of these elements would be desirable.     

Relative Sensitivity Distribution of Freshwater Planktonic Crustaceans to Trace Metals

Cladocerans and copepods are common inhabitants of ponds and lakes, but assessments of the toxic effects of chemicals on aquatic organisms are often based mainly on toxicity data for cladocerans of the genus Daphnia. The paucity of toxicity data for copepods and other species of cladocerans raised the question whether toxicity data derived primarily from daphniids can be extrapolated to protect other planktonic organisms. In this study, we address this question by systematically comparing between the sensitivities of cladocerans and copepods to the metals Cd, Cu, Pb, Ni, and Zn using the species sensitivity distributions. Our results indicate that cladocerans are consistently more sensitive than copepods to Cd and Cu. Most importantly, sensitivities of D. magna, D. pulex, and Ceriodaphnia dubia, the three most commonly tested cladocerans, to these metals are higher than those of most copepod species and fall within the range of those exhibited by other cladocerans. C. dubia, a cladoceran with relatively small body size, is more sensitive to all metals than most other cladoceran species. Our results imply that water quality criteria of trace metals derived from datasets dominated by Daphnia are likely also protective to copepods and most other cladocerans.