Metal Emissions Research Articles

Efficiency Assessment of the Production of Alternative Fuels of High Usable Quality within the Circular Economy: An Example from the Cement Sector

This article aims to present the mechanisms regulating the waste management system of one of the European countries that affect the cement industry. This publication analyses the possibility of using selected fractions of municipal and industrial waste as alternative fuels, including an analysis of ecological costs and benefits. The methodology includes the analysis of production data and the calculation of savings resulting from the use of alternative fuels. On this basis, ecological aspects were also indicated that should be taken into account when analyzing the profitability of the investment. Production data from an example Polish cement plant were used to analyze the research problem. Based on the guidelines of environmental standards and technical specifications, the parameters that PASr alternative fuels should meet were calculated in the company laboratory. This fuel type was then calculated in terms of emission intensity and production efficiency. The research results obtained in this paper study emphasize that the change in cement clinker production technology toward the use of waste raw materials and secondary fuels does not lead to an increase in heavy metal emissions to the extent that would justify qualifying cement as a material requiring systematic control of its harmful impacts on humans and the natural environment. The conclusions show that the use of alternative fuels reduces CO2 emissions and production costs, without negatively affecting the efficiency and production volume. The average energy requirement for the production of 1 ton of cement is approximately 3.3 GJ, which corresponds to 120 kg of coal with a calorific value of 27.5 MJ per kg. Energy costs account for 30–40% of the total cement production costs. Replacing alternative fuels with fossil fuels will help reduce energy costs, providing a competitive advantage for cement plants that use it as an energy source. The presented considerations can provide an answer to all interested parties, including representatives of the executive and legislative authorities, on what path the sector should follow to fit into the idea of sustainable building materials and the circular economy.

Emissivity of Metals of the Second Group of the Periodic Table

Emissivity of Metals of the Second Group of the Periodic Table

Mira Variables Based on Emission Lines in LAMOST DR9

We present a sample of 335 Mira variables, extracted from DR9 of the Large Sky Area Multi-Object Fiber Spectroscopic Telescope (LAMOST) survey. These variables are characterized by the Balmer emissions (Hδ, Hγ, Hβ, and Hα) and the metal emissions (Fe i λ λ 4202, 4308, 4376, and Mg i λ4571) observed in M giant spectra. We distinguished oxygen-rich stars from carbon-rich stars through the identification of carbon molecular bands present in the optical spectra. For the oxygen-rich stars we examined multiple attributes, such as the link between line strength and bolometric luminosity, and the connection between atmospheric parameters and their periods. We observed that Fe i λ λ 4202, 4308 showed a significantly gradual progression, which can be postulated to trace the fluorescent emission resulting from pulsation shocks. Regarding the correlation between T eff and the period, T eff remains relatively constant over varying periods, with no clear trend, while both log g and [Fe/H] show a decreasing trend within a period range of 450 days, and this decreasing of the log g trend is consistent with the results in the literature. To shed more light on the variations of Balmer lines, we showcase time-series spectra for two objects, demonstrating that the Balmer lines reach their peak intensity during the brightest phase of the stellar cycle.

Evidence for magnetic boundary layer accretion in RU Lup

Context. It is well established that classical T Tauri stars accrete material from a circumstellar disk through magnetic fields. However, the physics regulating the processes in the inner (0.1 AU) disk is still not well understood. Aims. Our aim is to characterize the accretion process of the classical T Tauri Star RU Lup. Methods. Optical high-resolution spectroscopic observations with CHIRON and ESPRESSO were obtained simultaneously with photometric data from AAVSO and TESS. Results. We detected a periodic modulation in the narrow component of the He I 5876 line with a period that is compatible with the stellar rotation period, indicating the presence of a compact region on the stellar surface that we identified as the footprint of the accretion shock. We show that this region is responsible for the veiling spectrum, which is made up of a continuum component plus narrow line emission that fills in the photospheric lines. An analysis of the high-cadence TESS light curve reveals quasi-periodic oscillations on timescales shorter than the stellar rotation period, suggesting that the accretion disk in RU Lup extends inward of the corotation radius, with a truncation radius at ~2 R*. This is compatible with predictions from three-dimensional magnetohydrodynamic models of accretion through a magnetic boundary layer (MBL). In this scenario, the photometric variability of RU Lup is produced by a nonsta-tionary hot spot on the stellar surface that rotates with the Keplerian period at the truncation radius. We also qualitatively discuss how more complex hot spot shapes may generate the same variability pattern. The analysis of the broad components of selected emission lines reveals the existence of a non-axisymmetric, temperature-stratified flow around the star, in which the gas leaves the accretion disk at the truncation radius and accretes onto the star channeled by the magnetic field lines. The unusually rich metallic emission line spectrum of RU Lup might be characteristic of the MBL regime of accretion. Conclusions. Our extensive multiwavelength database of RU Lup reveals many similarities to predictions from the scenario of accretion through a magnetic boundary layer. Alternative explanations would require the existence of a hot spot with a complex shape, perhaps made of two brighter knots, or a warped structure in the inner disk.

Metal concentration in honeybees along an urbanization gradient in Central Mexico

Urbanization is rapidly increasing worldwide, leading to rising levels of pollution, one of the major drivers of environmental change; yet little is known about the relationship between urbanization intensity and pollution levels in pollinator taxa. Toxic metals are among the most common contaminants in urban environments, but few data exist on their presence in the flora and fauna of cities in Latin America, one of the world's most urbanized and biologically diverse regions. In this study, we used an urban-rural gradient approach to analyze the relationship between the concentrations of eleven metals present in adult honeybees (Apis mellifera) and the degree of urbanization within twelve landscapes in the metropolitan area of Pachuca, Hidalgo, which forms part of the megalopolis of Mexico City. Metal concentrations were compared with previously reported values contrasting honeybees from urban and rural areas after standardizing urbanization levels among published reports. The concentrations of Ag, Cr, Cu, and Zn in honeybees increased significantly with the degree of urbanization. Urbanization was not found to influence the levels of Al, Ba, Cd, Mn, and Sr in honeybees. The maximum concentrations of six metals in our urban sites (Al, Ba, Cd, Cu, Mn, and Sr) were higher than the maximum values reported for bees in other urban areas. The concentrations of two metals measured in our study (Cr and Zn) were within the range of values previously published for urban areas. Compared to other studies, we did not detect Pb in the body of honeybees. We conclude that the concentrations of Ag, Cr, Cu, and Zn present in honeybees are a quantitative reflection of the degree of urbanization in central Mexico. Our results highlight the need to monitor metal emission sources in this and other areas and investigate their effects on bees and other pollinator taxa.

The emerging application of LC-based metallomics techniques to unravel the bioinorganic chemistry of toxic metal(loid)s

The on-going anthropogenic emission of toxic metal(loid) species into the environment contaminates the food supply and drinking water resources in various parts of the world. Given that inorganic pollutants cannot be degraded, their increased influx into the bloodstream of babies, children and pregnant women is inevitable. Since the ramifications of the ensuing environmental exposure on human health remain poorly defined, fundamentally new insight into their bioinorganic chemistry in organisms is urgently needed. Based on the flow of dietary constituents through organisms, the interaction of toxic metal(loid) species with biomolecules in the bloodstream deserve particular attention as they play an integral role in the mechanisms of their chronic toxicity. Gaining insight into these bioinorganic processes is hampered by the biological complexity of plasma/red blood cells and the low concentrations of the metal(loid) species of interest, but can be overcome by employing LC techniques hyphenated to atomic spectroscopic detectors (i.e. metallomics techniques). This perspective aims to highlight the potential of unconventional hyphenated separation modes to advance our understanding of the bioinorganic chemistry of toxic metal(loid) species in the bloodstream-organ system. Four examples are illustrated. The application of anion-exchange (AEX) and size-exclusion chromatography (SEC) provided new insight into the blood-based bioinorganic mechanisms that direct Cd2+ and MeHg+ to target organs. AEX chromatography also allowed to observe the formation of complexes between Hg2+ and MeHg+ with L-cysteine at pH 7.4, that are implicated in their organ uptake. Lastly, the application of reversed phase (RP) chromatography revealed a possible cytosolic mechanism by which N-acetyl-L-cysteine binds to MeHg+ in the presence of cytosolic glutathione (GSH). New insight into other bioinorganic processes may advance the regulatory framework to better protect public health.

Interactions between microplastics and heavy metals in leachate: Implications for landfill stabilization process

The emission of microplastics and heavy metals in landfills has attracted widespread attention for its stabilization process. Microplastics have become carriers of heavy metals due to their adsorption properties, affecting their environmental behavior. However, the effects of landfill stabilization on the interaction between microplastics and heavy metals in leachate are ambiguous. This work explored the abundance characteristics of microplastics and heavy metals in leachate from 10 landfills in Beijing. Overall, the average abundance of microplastics was 196.3 items/L, dominated by small particle size (20–50 µm) and film microplastics. The levels of Cr and As were much higher than other heavy metals. The average abundance of microplastics and polymer types tended to decrease as the landfill stabilization proceeded, and the surface composition of microplastics became more complex. Statistical analysis revealed that the correlations between microplastics and heavy metals in the leachate of landfill stabilization presented significant parabolic characteristics, and Cr and As were more susceptible to landfill stabilization with significant positive correlation with a wide range of microplastics such as 20–30 µm. These results were intended to provide a scientific basis for the treatment and disposal of waste leachate and the synergistic prevention and control of new and traditional pollutants.

Source apportionment and emission projections of heavy metals from traffic sources in India: Insights from elemental and Pb isotopic compositions

The study investigates the sources of metals in urban road dusts using elemental concentration and Pb isotopic ratios. The elemental concentrations are also utilized to determine the present heavy metal emissions as well as projected emissions till 2045. Bayesian mixing model for source apportionment highlights the significant contributions of both exhaust and non-exhaust sources to the metal-enriched urban road dusts, with each contributing approximately 40 %. Emission analysis reveals that India’s projected electric vehicle (EV) penetration may not be sufficient to suppress the metal emissions from vehicular exhausts. Further challenge is posed by high metal concentrations in the non-exhaust sources, that dominates the emission of some metals compared to exhaust sources. If the metal concentrations remain unchanged, the emission analysis predicts alarming increases in total emissions from all the exhaust and non-exhaust sources by 174 %, 176 %, 163 % and 184 % for Ni, Cu, Zn and Pb, respectively, from 2022 to 2045. Thus, it is crucial to reduce the metal concentrations in traffic emission sources and also impose better regulatory measures to improve the urban metal pollution scenario.

Heterogeneous evolution and driving forces of multiple hazardous air pollutants and GHGs emissions from China's primary aluminum industry

The booming of China's primary aluminum industry (PAI) brought substantial emissions of hazardous air pollutants (HAPs) and greenhouse gases (GHGs). By using life cycle assessment and bottom-up method, a comprehensive emission inventory for multiple typical HAPs and GHGs from China's PAI during 1990–2021 was developed and explored for the first time. Our results show that spatial-temporal emissions trends of HAPs and GHGs from PAI in China diverse significantly. The conventional atmospheric pollutants (including SO2, NOx and particulate matter (PM)), fluoride and per fluorinated compound (PFCs) had been effectively suppressed since 2007 due to the implementation of various environmental policies; while, emissions of CO, VOCs, CH4, heavy metals and CO2 had increased at different rates unexpectedly. From the spatial distribution perspective, Henan, Shanxi, Guizhou, Guangxi and Shandong dominated the emissions of PAI in China, but with consumption expansion and environmental constrains, PAI plants start to expand to northwest and southwest areas where are richer in sufficient and cheaper power resources, thus bring significant emission increasing there, particular for conventional atmospheric pollutants in northwest and CO and VOCs in southwest China. By underlying driving forces of PAI emissions, results show that end-of-pipe control measures at various stages have played different roles to reduce emissions of the concerned species at each period, but its reduction effect diminished gradually. Future reduction should seek underlying changes in production technology and energy system. Under constrains of environmental regulation and resource endowment, promoting circular economic development for PAI would be a key strategy to reduce HAPs and GHGs emissions simultaneously in PAI.

Trends in sedimentary Cladocera and metal(loid)s from Williams Lake (Washington, USA) track ∼125 years of trans-boundary contamination from smelter emissions in the upper Columbia River valley

The lead‑zinc smelter at Trail (British Columbia, Canada) has operated continuously for ∼125 years, with long-standing concerns that transboundary metal(loid) and sulphur emissions have contaminated water bodies in both western Canada and Washington (WA), USA. To assess aquatic ecosystems affected by over a century of industrial contamination requires an understanding of pre-smelting conditions. Here, we use a dated sediment core from Williams Lake (WA), downwind of both the Trail and the short-lived LeRoi (Northport, WA) smelters, to track regional contaminant history and other environmental stressors. Specifically, we examine a selection of chemical elements, cladoceran assemblages, visible range spectroscopy-inferred chlorophyll a (VRS-Chl a) and visible near-infrared spectroscopy-inferred lake-water total organic carbon (VNIRS-TOC). Sedimentary proxies recorded the onset of smelting in 1896 CE, peak periods of aerial emissions in the early to mid-20th century, and the history of emission controls. With a few exceptions, sedimentary metal(loid)s exceeded Canadian Interim Sediment Quality Guidelines during the height of the smelting era and have declined substantially since ca. 2000 CE. The loss of metal-sensitive Cladocera and declines in primary production (VRS-Chl a) at the onset of the regional smelting era indicate a strong biological response to airborne industrial contamination. The largest cladoceran change in the sediment record was concurrent with accelerated mitigation efforts at the Trail facilities following the 1960s; however, this compositional shift was between ecologically similar daphniid taxa. Steep declines in VNIRS-TOC concentrations during the period of peak emissions at Trail suggested an increase in sulphur deposition on the landscape that reduced terrestrial carbon supply. However, the persistence of calcium-sensitive daphniids throughout the record indicates that alkaline Williams Lake had not acidified. Current cladoceran assemblages remain substantially distinct from pre-industrial communities, demonstrating how paleoecotoxicological approaches can be used to track the effects of multiple stressors in a temporally appropriate context.

Exploring the characteristics and source-attributed health risks associated with polycyclic aromatic hydrocarbons and metal elements in atmospheric PM2.5 during warm and cold periods in the northern metropolitan area of Taiwan

Polycyclic aromatic hydrocarbons (PAHs) and metal elements are commonly considered hazardous air pollutants due to their toxic, mutagenic, and carcinogenic properties. However, few studies have simultaneously examined their potential sources and health effects. This study aimed to quantify the PAHs and metal elements in atmospheric PM2.5, investigating their characteristics and potential sources to assess associated health risks in the northern metropolitan area of Taiwan. The measurements indicated that the mean concentrations of total PAHs and metal elements in PM2.5 were 0.97 ± 0.52 ng m−3 and 590 ± 200 ng m−3, respectively. Utilizing the positive matrix factorization profiles, the PAH pollution was classified into two sources: industrial emissions, traffic emissions, and coal combustion (69%) were the predominant sources of PAHs, with petroleum volatilization and biomass burning (31%) making a lesser contribution. Similarly, we traced metal elements to three potential sources: natural sources (48%), a combined source of industrial emissions, coal combustion, and traffic exhaust (32%), and a blend of non-exhaust emissions from traffic and waste incineration sources (20%). Results from the potential source contribution function model suggested that the emissions of PAHs and metals could be influenced by the eastern regions of China, although local sources, including waste incinerators, traffic, shipping, and harbor activities, were identified as the primary contributors. Source-attributed excess cancer risk revealed that industry, traffic, and coal combustion had the highest cancer risk posed by PAHs in the cold period (1.0 × 10−5), while the greatest cancer risk among metal elements was linked to non-exhaust emissions from traffic and waste incineration emissions (2.0 × 10−5). This research underscores the importance of considering source contributions to health risk and emission reduction when addressing PM2.5 pollution. These findings have direct implications for policymakers, providing them with valuable insights to develop strategies that protect public health from the detrimental effects of PAH and metal element exposure.

On the Doublet Flux Ratio of Mg ii Resonance Lines in and Around Galaxies

Observations of metallic doublet emission lines, particularly Mg ii λ λ2796, 2803, provide crucial information for understanding galaxies and their circumgalactic medium. This study explores the effects of resonant scattering on the Mg ii doublet lines and the stellar continuum in spherical and cylindrical geometries. Our findings show that under certain circumstances, resonance scattering can cause an increase in the doublet flux ratio and the escaping flux of the lines beyond what is expected in optically thin spherical media. As expected, the doublet ratio is consistently lower than the intrinsic ratio when the scattering medium is spherically symmetric and dusty. However, if the scattering medium has a disk shape, such as face-on disk galaxies, and is viewed face-on, the doublet ratio is predicted to be higher than 2. It is also shown that doublet ratios as low as those observed in compact star-forming galaxies cannot be explained solely by pure dust attenuation of intrinsic Mg ii emission lines in spherical models unless dust opacity deviates markedly from that expected based on the dust-to-Mg+ gas ratio of our Galaxy. The importance of the continuum-pumped emission lines and expanding media is discussed to understand observational aspects, including doublet flux ratios, which can be lower than 1.5 or higher than 2, as well as symmetric or asymmetric line profiles. It is also discussed that the diffuse warm neutral medium may be an important source of Mg ii emission. These results provide insight into the complexity of the shape and orientation of distant, spatially unresolved galaxies.

Mathematical-model Analysis of the Potential Exposure to Lead, Zinc and Iron Emissions from Consumption of Premium Motor Spirit in Nigeria

Environmental pollution has been on the increase due to emission from vehicles using fossil fuels. This research investigated the exposure of air, soil and water bodies to trace metal emissions: Pb, Zn and Fe, as a result of the consumption of premium motor spirit (PMS) in Nigeria. The exposure of air, soil, and water bodies to these emissions also lead to exposure of humans, food and animals to the emissions. This was done to estimate the emission rates, emission rate per capita, and emission rates per land areas (or land distribution). The results showed that: the annual emission rates ranged between 4.66 kg/y for Pb in 2012 in Jigawa State and 5.050∙103 kg/y for Fe in 2015 in Lagos State; the emission rates per capita ranged between 0.52∙10−6 kg/(y∙person) for Pb in 2012 in Kwara State and 2.33∙10−3 kg/(y∙person) and this was recorded in Lagos State in the year 2015; while the rate per land area ranged between 0.093∙10−3 kg/(y∙km2) for Pb in 2012 in Taraba State and 1.38 kg/(y∙km2) for Fe in 2015 in Lagos State. Results showed that residents of Lagos are at the highest risk of trace metal poisoning because they had the highest emission rates per capita, followed by Abuja, Osun, and Ogun. The states at the lowest risk are Yobe and Taraba, with Yobe as the lowest. It is recommended that regulations concerning the trace metal contents of fuels imported and distributed in Nigeria should be created and implemented to curb these risks.

Atmospheric emissions of particulate matter-bound heavy metals from industrial sources

Although industrial activities are significant contributors to atmospheric releases of particulate matter (PM) and associated toxic substances that lead to adverse human health effects, a knowledge gap exists concerning the human health risk resulting from such activities owing to lack of evaluation of industrial emissions. Here, we comprehensively characterized and quantified PM from 118 full-scale industrial plants. The dominant (97.9 %) PM showed diameters of <2.5 μm; 79.0 % had diameters below 1 μm. Annual atmospheric releases of Fe and heavy metals (As, Cd, Cr, Cu, Ni, Pb, Zn) contained in fine PM from these global industrial activities are estimated to be 51,161 t and 69,591 t, respectively. Emissions of heavy metals from these industries cause increased cancer risk, estimated to range from 1461 % to 50,752 %. Five crystalline compounds (ZnO, PbSO4, Mn3O4, Fe3O4, Fe2O3) that can indicate specific industrial sources are identified. Global annual emissions of these toxic compounds in fine PM from the industrial sources are estimated to be 78,635 t. The Global South displayed higher emissions than the Global North. These results are significant for recognizing regional health risks of industrial emissions.

Global scenarios of anthropogenic mercury emissions

Abstract. Anthropogenic mercury (Hg) emissions to the atmosphere are a long-lived hazard to human and environmental health. The UN Minamata Convention on Mercury is seeking to lower anthropogenic mercury emissions through a mix of policies from banning certain Hg uses to reducing unintentional Hg release from different activities. In addition to independent Hg policy, strategies to mitigate greenhouse gases, particulate matter (PM) and SO2 may also lower Hg emissions as a co-benefit. This study uses the Greenhouse Gas–Air Pollution Interactions and Synergies (GAINS) model to examine the effect of different clean air and climate policies on future global Hg emissions. The baseline scenario assumes current trends for energy use and Hg emissions as well as current legislation for clean air, mercury and climate policy. In addition, we explore the impact of the Minamata Convention, the co-benefits of climate and stringent air pollution policies, and maximum feasible reduction measures for Hg. Hg emission projections until 2050 show noticeable reductions in combustion sectors for all scenarios due to a decrease in global fossil fuel and traditional biomass use, leading to emission reductions of 33 % at baseline and up to 90 % when combining stringent climate controls and the most efficient Hg controls. Cement and non-ferrous metal emissions increase in all scenarios with current air pollution policy but could be reduced by up to 72 % and 46 %, respectively, in 2050 with stringent Hg-specific measures. Other emissions (including waste) are a significant source of uncertainty in this study, and their projections range between a 22 % increase and a 54 % decrease in 2050, depending on both climate and clean air policy. The largest absolute reduction potential for Hg abatement but also the largest uncertainties regarding absolute emissions lie in small-scale and artisanal gold production, where abatement measures could eliminate annual Hg emissions in the range of 601–1371 t (95 % confidence interval), although the uncertainties in the estimate are so high that they might eclipse reduction efforts in all other sectors. In total, 90 % of Hg emissions are covered by provisions of the Minamata Convention. Overall, the findings emphasize the necessity to implement targeted Hg control policies in addition to stringent climate, PM and SO2 policies to achieve significant reductions in Hg emissions.

Author Correction: Unveiling long-lived dual emission in a tetraphenylethylene-based metal–organic framework

Author Correction: Unveiling long-lived dual emission in a tetraphenylethylene-based metal–organic framework

Dwarf galaxy merger-induced star formation rate: A case study of Mrk 1481

The merger of the galaxies serves as a trigger for the increase in the galaxy’s star formation rate (SFR), which can be quantified by observing the column density of the Hα line. Our findings report the presence of various gas and metal emission lines, strongly indicating that the galaxy hosts very young stars and is currently undergoing active star formation processes. Notably, we report a relatively high SFR of ∼ 0.0055 M⊙ yr-1 for a dwarf galaxy, alongside a metallicity level of 12 + log(O/H) ∼ 8.88 dex. Our photometric analysis reinforces the notion that the galaxy is in the midst of a merger phase. Additionally, the analysis indicates that the galaxy has a relatively flat shape (Sérsic index ∼ 0.8), with stars distributed more broadly and less concentrated toward its center. This provides further evidence of the ongoing merger and its impact on the galaxy’s structure. The half-life radius of the galaxy is estimated to be 2.73 arcsec by using the Petrosian method.

Copper, Iron, Cadmium, and Arsenic, All Generated in the Universe: Elucidating Their Environmental Impact Risk on Human Health Including Clinical Liver Injury.

Humans are continuously exposed to various heavy metals including copper, iron, cadmium, and arsenic, which were specifically selected for the current analysis because they are among the most frequently encountered environmental mankind and industrial pollutants potentially causing human health hazards and liver injury. So far, these issues were poorly assessed and remained a matter of debate, also due to inconsistent results. The aim of the actual report is to thoroughly analyze the positive as well as negative effects of these four heavy metals on human health. Copper and iron are correctly viewed as pollutant elements essential for maintaining human health because they are part of important enzymes and metabolic pathways. Healthy individuals are prepared through various genetically based mechanisms to maintain cellular copper and iron homeostasis, thereby circumventing or reducing hazardous liver and organ injury due to excessive amounts of these metals continuously entering the human body. In a few humans with gene aberration, however, liver and organ injury may develop because excessively accumulated copper can lead to Wilson disease and substantial iron deposition to hemochromatosis. At the molecular level, toxicities of some heavy metals are traced back to the Haber Weiss and Fenton reactions involving reactive oxygen species formed in the course of oxidative stress. On the other hand, cellular homeostasis for cadmium and arsenic cannot be provided, causing their life-long excessive deposition in the liver and other organs. Consequently, cadmium and arsenic represent health hazards leading to higher disability-adjusted life years and increased mortality rates due to cancer and non-cancer diseases. For unknown reasons, however, liver injury in humans exposed to cadmium and arsenic is rarely observed. In sum, copper and iron are good for the human health of most individuals except for those with Wilson disease or hemochromatosis at risk of liver injury through radical formation, while cadmium and arsenic lack any beneficial effects but rather are potentially hazardous to human health with a focus on increased disability potential and risk for cancer. Primary efforts should focus on reducing the industrial emission of hazardous heavy metals.

A Luminescent Hybrid Bimetallic Halide Family with Solvent‐Coordinated Rare Earth and Alkaline Earth Metals

AbstractHybrid metal halides are an extraordinary class of optoelectronic materials with extensive applications. To further diversify and study the in‐depth structure‐property relations, we report here a new family of 21 zero‐dimensional hybrid bimetallic chlorides with the general formula A(L)n[BClm] (A=rare earth (RE), alkaline earth metals and Mn; L=solvent ligand; and B=Sb, Bi and Te). The RE(DMSO)8[BCl6] (RE=La, Ce, Sm, Eu, Tb, and Dy; DMSO=dimethyl sulfoxide) series shows broadband emission attributed to triplet radiative recombination from Sb and Bi, incorporating the characteristic emission of RE metals, where Eu(DMSO)8[BiCl6] shows a staggering PL quantum yield of 94 %. The pseudo‐octahedral [SbCl5] with Cl vacancy in AII(DMSO)6[SbCl5] (AII=Mg, Ca and Mn) and the square pyramidal [SbCl5] in AII(TMSO)6[SbCl5] (TMSO=tetramethylene sulfoxide) enhance the stereoactive expression of the 5 s2 lone pairs of Sb3+, giving rise to the observation of dual‐band emission of singlet and triplet emission, respectively. A series of Te(IV) analogues have been characterized, showing blue‐light‐excitable single‐band emission. This work expands the materials space for hybrid bimetallic halides with an emphasis on harnessing the RE elements, and provides important insights into designing new emitters and regulating their properties.

A Luminescent Hybrid Bimetallic Halide Family with Solvent-Coordinated Rare Earth and Alkaline Earth Metals.

Hybrid metal halides are an extraordinary class of optoelectronic materials with extensive applications. To further diversify and study the in-depth structure-property relations, we report here a new family of 21 zero-dimensional hybrid bimetallic chlorides with the general formula A(L)n[BClm] (A=rare earth (RE), alkaline earth metals and Mn; L=solvent ligand; and B=Sb, Bi and Te). The RE(DMSO)8[BCl6] (RE=La, Ce, Sm, Eu, Tb, and Dy; DMSO=dimethyl sulfoxide) series shows broadband emission attributed to triplet radiative recombination from Sb and Bi, incorporating the characteristic emission of RE metals, where Eu(DMSO)8[BiCl6] shows a staggering PL quantum yield of 94 %. The pseudo-octahedral [SbCl5] with Cl vacancy in AII(DMSO)6[SbCl5] (AII=Mg, Ca and Mn) and the square pyramidal [SbCl5] in AII(TMSO)6[SbCl5] (TMSO=tetramethylene sulfoxide) enhance the stereoactive expression of the 5 s2 lone pairs of Sb3+, giving rise to the observation of dual-band emission of singlet and triplet emission, respectively. A series of Te(IV) analogues have been characterized, showing blue-light-excitable single-band emission. This work expands the materials space for hybrid bimetallic halides with an emphasis on harnessing the RE elements, and provides important insights into designing new emitters and regulating their properties.