Pub Date : 2024-11-14DOI: 10.1016/j.envint.2024.109146
Nathan R. Gray, Alastair C. Lewis, Sarah J. Moller
Macro-scale distribution of air pollution concentrations is influenced by factors including geography, weather, industry, transport and regulation. Pollution sources are unevenly distributed, with some communities disproportionately impacted by higher emissions. This study separates the effects of deprivation from ethnicity as factors that influence proximity to pollution sources. We combine recent decadal census data (2021) on socioeconomic deprivation and detailed population ethnicity at fine scales (Lower Super Output layer Area, LSOA n = 1600 people) with a 1×1 km sector-resolved atmospheric emissions inventory for NOx and primary PM2.5 in England. All 24 minoritised ethnic groups studied experienced higher average local NOx and PM2.5 emissions than socio-economically matched populations in the majority ‘White: English, Welsh, Scottish, Northern Irish or British‘ ethnic group. Chinese, Arab and Bangladeshi communities experienced the largest disparity in NOx, with weighted emissions 100 %, 91 %, 89 % higher than white populations of matched deprivation status. Bangladeshi, Pakistani and Roma groups experienced on average 40 %, 40 %, 36 % higher PM2.5 emissions locally than matched white groups. For NOx the largest contributors leading to disparity, were road transport (48 %), domestic combustion (23 %) and industry (15 %). For PM2.5 the greatest contributors to disparity were domestic combustion (53 %), road transport (19 %), and industry (11 %). Living near to road transport and in city centres are frequently cited as primary drivers of ethnicity and deprivation-based disparities, however the analysis identifies that industrial, domestic and off-road sources create issues of the same magnitude, and disparities remain in suburban settings, smaller towns and some rural areas.
{"title":"Evaluating disparities in air pollution as a function of ethnicity, deprivation and sectoral emissions in England","authors":"Nathan R. Gray, Alastair C. Lewis, Sarah J. Moller","doi":"10.1016/j.envint.2024.109146","DOIUrl":"https://doi.org/10.1016/j.envint.2024.109146","url":null,"abstract":"Macro-scale distribution of air pollution concentrations is influenced by factors including geography, weather, industry, transport and regulation. Pollution sources are unevenly distributed, with some communities disproportionately impacted by higher emissions. This study separates the effects of deprivation from ethnicity as factors that influence proximity to pollution sources. We combine recent decadal census data (2021) on socioeconomic deprivation and detailed population ethnicity at fine scales (Lower Super Output layer Area, LSOA n = 1600 people) with a 1×1 km sector-resolved atmospheric emissions inventory for NO<sub>x</sub> and primary PM<sub>2.5</sub> in England. All 24 minoritised ethnic groups studied experienced higher average local NO<sub>x</sub> and PM<sub>2.5</sub> emissions than socio-economically matched populations in the majority ‘White: English, Welsh, Scottish, Northern Irish or British‘ ethnic group. Chinese, Arab and Bangladeshi communities experienced the largest disparity in NO<sub>x</sub>, with weighted emissions 100 %, 91 %, 89 % higher than white populations of matched deprivation status. Bangladeshi, Pakistani and Roma groups experienced on average 40 %, 40 %, 36 % higher PM<sub>2.5</sub> emissions locally than matched white groups. For NO<sub>x</sub> the largest contributors leading to disparity, were road transport (48 %), domestic combustion (23 %) and industry (15 %). For PM<sub>2.5</sub> the greatest contributors to disparity were domestic combustion (53 %), road transport (19 %), and industry (11 %). Living near to road transport and in city centres are frequently cited as primary drivers of ethnicity and deprivation-based disparities, however the analysis identifies that industrial, domestic and off-road sources create issues of the same magnitude, and disparities remain in suburban settings, smaller towns and some rural areas.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"46 1","pages":""},"PeriodicalIF":11.8,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610495","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-14DOI: 10.1016/j.envint.2024.109142
Shunyao Wang, Ran Tu
We appreciate Dr. Canu for the helpful comments on our recent review paper “Indoor air quality in sub microenvironments: Pollutant characteristics, adverse health impacts, and population inequality”. We have carefully considered each point that Dr. Canu raised and will take this opportunity to clarify the references in this review for a better understanding of our study.
{"title":"Reply to Canu: Correspondence with reference to the review “Indoor Air Quality in Subway Microenvironments”","authors":"Shunyao Wang, Ran Tu","doi":"10.1016/j.envint.2024.109142","DOIUrl":"https://doi.org/10.1016/j.envint.2024.109142","url":null,"abstract":"We appreciate Dr. Canu for the helpful comments on our recent review paper “Indoor air quality in sub microenvironments: Pollutant characteristics, adverse health impacts, and population inequality”. We have carefully considered each point that Dr. Canu raised and will take this opportunity to clarify the references in this review for a better understanding of our study.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"127 1","pages":""},"PeriodicalIF":11.8,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610494","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Julian Fanghanel, Satoshi Yokomizo, Shuichi Funahashi, Clive A Randall
In this paper we successfully densified NiMn2O4 (NMO) ceramics using the cold sintering process (CSP) with various molten salt fluxes as a transient liquid phase, achieving relative densities exceeding 95%. The resulting samples exhibited comparable properties to conventionally sintered counterparts, demonstrating the feasibility of the CSP for NMO thermistor production. Electrical characterization revealed NMO samples sintered via CSP exhibited NTC behavior with material constants (β) and temperature coefficients of resistivity (α) akin to conventionally sintered materials in the range of 3500-4300 K and 0.04-0.05 K-1. Despite slightly higher resistances attributed to differences in grain size and impurities, the CSP-produced NMO samples remained within the typical range for NTC thermistors.
{"title":"Cold Sintering of Nickel Manganese Oxide for Thermistors Fabrication","authors":"Julian Fanghanel, Satoshi Yokomizo, Shuichi Funahashi, Clive A Randall","doi":"10.1039/d4ta06380e","DOIUrl":"https://doi.org/10.1039/d4ta06380e","url":null,"abstract":"In this paper we successfully densified NiMn<small><sub>2</sub></small>O<small><sub>4</sub></small> (NMO) ceramics using the cold sintering process (CSP) with various molten salt fluxes as a transient liquid phase, achieving relative densities exceeding 95%. The resulting samples exhibited comparable properties to conventionally sintered counterparts, demonstrating the feasibility of the CSP for NMO thermistor production. Electrical characterization revealed NMO samples sintered via CSP exhibited NTC behavior with material constants (β) and temperature coefficients of resistivity (α) akin to conventionally sintered materials in the range of 3500-4300 K and 0.04-0.05 K-1. Despite slightly higher resistances attributed to differences in grain size and impurities, the CSP-produced NMO samples remained within the typical range for NTC thermistors.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"108 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610094","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Scott D. George, Adam J. Sepulveda, Patrick R. Hutchins, David S. Pilliod, Katy E. Klymus, Austen C. Thomas, Ben C. Augustine, Chany C. Huddleston Adrianza, Devin N. Jones, Jacob R. Williams, Eric G. Leinonen
Environmental DNA (eDNA) analysis has become a transformative technology, but sample collection methods lack standardization and sampling at effective frequencies requires considerable field effort. Autonomous eDNA samplers that can sample water at high frequencies offer potential solutions to these problems. We present results from four case studies using a prototype autonomous eDNA sampler as part of the U.S. Geological Survey’s Rapid Environmental eDNA Assessment and Deployment Initiative & Network (READI-Net) project. These case studies involved short-term deployments of an eDNA autosampler (Smith-Root) across a range of riverine habitats with the objectives of (a) identifying what insights could be gained from high-frequency autosampling and (b) benchmarking these autosamples against manually collected samples. The high frequency autosampling revealed high temporal variability of eDNA concentrations and provided valuable insights about eDNA associations with environmental covariates, such as discharge and turbidity. Benchmarking assessments indicated autosamples had similar detection rates to manual samples and obtained similar or greater eDNA quantities. We did find minimal carryover contamination in autosampler field controls. We conclude that eDNA autosamplers have potential to improve freshwater biosurveillance by reducing logistical sampling barriers, standardizing collection methods, and clarifying the influence of environmental covariates on eDNA results.
{"title":"Field Trials of an Autonomous eDNA Sampler in Lotic Waters","authors":"Scott D. George, Adam J. Sepulveda, Patrick R. Hutchins, David S. Pilliod, Katy E. Klymus, Austen C. Thomas, Ben C. Augustine, Chany C. Huddleston Adrianza, Devin N. Jones, Jacob R. Williams, Eric G. Leinonen","doi":"10.1021/acs.est.4c04970","DOIUrl":"https://doi.org/10.1021/acs.est.4c04970","url":null,"abstract":"Environmental DNA (eDNA) analysis has become a transformative technology, but sample collection methods lack standardization and sampling at effective frequencies requires considerable field effort. Autonomous eDNA samplers that can sample water at high frequencies offer potential solutions to these problems. We present results from four case studies using a prototype autonomous eDNA sampler as part of the U.S. Geological Survey’s Rapid Environmental eDNA Assessment and Deployment Initiative & Network (READI-Net) project. These case studies involved short-term deployments of an eDNA autosampler (Smith-Root) across a range of riverine habitats with the objectives of (a) identifying what insights could be gained from high-frequency autosampling and (b) benchmarking these autosamples against manually collected samples. The high frequency autosampling revealed high temporal variability of eDNA concentrations and provided valuable insights about eDNA associations with environmental covariates, such as discharge and turbidity. Benchmarking assessments indicated autosamples had similar detection rates to manual samples and obtained similar or greater eDNA quantities. We did find minimal carryover contamination in autosampler field controls. We conclude that eDNA autosamplers have potential to improve freshwater biosurveillance by reducing logistical sampling barriers, standardizing collection methods, and clarifying the influence of environmental covariates on eDNA results.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"42 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610493","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
<p>The resistance and resilience of ecosystems to disturbance and change are astonishing; however, all good things eventually have an end. Depending on the severity of the disturbance, the ecosystems' ability to balance these disturbances dwindles, and well-established systems can crash. Introductions of foreign animals into ecosystems happen around the world, in every environment, and can lead to drastic consequences—though not all negative—within the recipient ecosystem (Chaffin et al. <span>2016</span>). So-called “alien species” or “invasive alien species” (IAS) can stem from virtually all organism groups, and while not all newly introduced species become problematic, some of them establish functioning populations, can dominate over native species, and lead to major disruptions of ecosystem functioning, local species extinction, or act as vectors of diseases (Colautti and MacIsaac <span>2004</span>; Crowl et al. <span>2008</span>).</p><p>Among the groups which can have a great impact on recipient ecosystems are fish, with almost 200 recorded introduced species in Europe as of today (Carpio et al. <span>2019</span>). Although animal migrations can lead to natural species displacements, human actions are responsible for many modern-day introduction events. Relevant vectors for fish introductions can include fishery or release of ornamental pet fish (Carpio et al. <span>2019</span>). Goldfish, <i>Carassius auratus</i>, are among the most used and beloved pet fish, being sold around the globe to be kept in fish bowls, aquariums, and garden ponds. The consequences of the release of these ornamental pets which to many people, are just “small colorful fish” in natural systems can be drastic. There are multiple reasons why goldfish are the ideal candidate for being a “successful” IAS. Goldfish, stemming from the same family (Cyprinidae) as the well-known carp, are extremely resilient to adverse environmental conditions, and, as omnivorous fish, eat virtually anything in their vicinity such as aquatic plants, or insect larvae. What seems so harmless to our eyes when swimming in our indoor aquarium is indeed a perfect killing machine when left to do as they please.</p><p>In their original research article, combining an eco-functional approach and food web modelling based on taxonomic, functional, and stable isotopes analysis, Lejeune, Lepoint, and Denoël (<span>2024</span>) delve into the devastating effects of introduced goldfish as predators in the food webs of naturally fishless permanent ponds in France. Historically, these ponds harbored palmate newts as their dominant amphibian predator, which suffered subsequent exclusion from the ponds after fish introduction. In ponds that feature goldfish, only a third of the consumer communities' richness persevered, which makes the extent of simplification of the entire food web evident. Additionally, reduced food chain length and the prevalence of detritus-feeding groups in ponds with introduced fish, seve
{"title":"Beautiful Killers—The Goldfish Effect","authors":"Lena Fehlinger","doi":"10.1111/gcb.17582","DOIUrl":"10.1111/gcb.17582","url":null,"abstract":"<p>The resistance and resilience of ecosystems to disturbance and change are astonishing; however, all good things eventually have an end. Depending on the severity of the disturbance, the ecosystems' ability to balance these disturbances dwindles, and well-established systems can crash. Introductions of foreign animals into ecosystems happen around the world, in every environment, and can lead to drastic consequences—though not all negative—within the recipient ecosystem (Chaffin et al. <span>2016</span>). So-called “alien species” or “invasive alien species” (IAS) can stem from virtually all organism groups, and while not all newly introduced species become problematic, some of them establish functioning populations, can dominate over native species, and lead to major disruptions of ecosystem functioning, local species extinction, or act as vectors of diseases (Colautti and MacIsaac <span>2004</span>; Crowl et al. <span>2008</span>).</p><p>Among the groups which can have a great impact on recipient ecosystems are fish, with almost 200 recorded introduced species in Europe as of today (Carpio et al. <span>2019</span>). Although animal migrations can lead to natural species displacements, human actions are responsible for many modern-day introduction events. Relevant vectors for fish introductions can include fishery or release of ornamental pet fish (Carpio et al. <span>2019</span>). Goldfish, <i>Carassius auratus</i>, are among the most used and beloved pet fish, being sold around the globe to be kept in fish bowls, aquariums, and garden ponds. The consequences of the release of these ornamental pets which to many people, are just “small colorful fish” in natural systems can be drastic. There are multiple reasons why goldfish are the ideal candidate for being a “successful” IAS. Goldfish, stemming from the same family (Cyprinidae) as the well-known carp, are extremely resilient to adverse environmental conditions, and, as omnivorous fish, eat virtually anything in their vicinity such as aquatic plants, or insect larvae. What seems so harmless to our eyes when swimming in our indoor aquarium is indeed a perfect killing machine when left to do as they please.</p><p>In their original research article, combining an eco-functional approach and food web modelling based on taxonomic, functional, and stable isotopes analysis, Lejeune, Lepoint, and Denoël (<span>2024</span>) delve into the devastating effects of introduced goldfish as predators in the food webs of naturally fishless permanent ponds in France. Historically, these ponds harbored palmate newts as their dominant amphibian predator, which suffered subsequent exclusion from the ponds after fish introduction. In ponds that feature goldfish, only a third of the consumer communities' richness persevered, which makes the extent of simplification of the entire food web evident. Additionally, reduced food chain length and the prevalence of detritus-feeding groups in ponds with introduced fish, seve","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"30 11","pages":""},"PeriodicalIF":10.8,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1111/gcb.17582","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610472","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Feng Qiu, Chunyan Li, Xiaodong Xuan, Senhe Huang, Chenbao Lu, Hualin Lin, Sheng Han, Xiao-Dong Zhuang, Wai-Yeung Raymond Wong
Conjugated microporous polymers (CMPs) with π-conjugated framework, inherent porosity and tunable structure have been considered as the promising platforms as electrocatalysts for carbon dioxide reduction reaction (CO2RR). Promoting the proton transfer dynamic to modulate microenvironment of active sites in CMPs plays an important role on the improvement of their electrocatalytic activity. Herein, we developed a series of novel porphyrinic conjugated microporous polyanilines (CMPANI-n) constructed from tetrabromo-cobalt(II) porphyrin and diamino aromatics by the Buchwald–Hartwig coupling polymerization approach. Owing to the three-dimensional geometry of these polymeric skeleton, microenvironment of catalytic CoN4 site could be readily regulated by incorporation of nitrogen-doped diamino aromatic, leading to the enhancement of electrocatalytic activity for the carbon monoxide (CO) production. Notably, pyrazine-containing CMPANI (CMPANI-3) shows the high CO Faradaic efficiency (FECO) (97 % at −0.7 V vs. RHE), excellent turnover frequency (TOF) (2264 h−1 at −0.7 V vs. RHE) and large current density (>200 mA cm−2). The kinetic isotope effect results indicate that the pyrazinyl-N in CMPANI-3 facilitates the efficient proton absorption and transfer. Moreover, in-situ Fourier transform infrared spectra demonstrate that the protonated pyrazinyl-N would promote the generation and stabilization of *COOH intermediate via the coordination interaction around CoN4 site, thus favoring the electroreduction of CO2-to-CO conversion. This work provides a new sight in the design of polymeric electrocatalyst system with superior electron and proton transport for boosting CO2RR applications.
具有π-共轭框架、固有孔隙率和可调结构的共轭微孔聚合物（CMPs）已被视为二氧化碳还原反应（CO2RR）的电催化剂平台，前景广阔。促进质子传递动力学以调节 CMPs 中活性位点的微环境对提高其电催化活性具有重要作用。在此，我们开发了一系列新型卟啉共轭微孔聚苯胺（CMPANI-n），它们是由四溴钴(II)卟啉和二氨基芳烃通过布赫瓦尔德-哈特维格偶联聚合法构建而成。由于这些聚合物骨架的三维几何形状，催化 CoN4 位点的微环境可通过加入掺氮的二氨基芳香族化合物进行调节，从而提高了一氧化碳（CO）生成的电催化活性。值得注意的是，含吡嗪的 CMPANI（CMPANI-3）显示出较高的一氧化碳法拉第效率（FECO）（-0.7 V 对 RHE 时为 97 %）、出色的周转频率（TOF）（-0.7 V 对 RHE 时为 2264 h-1）和较大的电流密度（>200 mA cm-2）。动力学同位素效应结果表明，CMPANI-3 中的吡嗪基-N 促进了质子的有效吸收和转移。此外，原位傅立叶变换红外光谱表明，质子化的吡嗪基-N 会通过 CoN4 位点周围的配位相互作用促进 *COOH 中间体的生成和稳定，从而有利于 CO2 到 CO 的电还原转化。这项工作为设计具有优异电子和质子传输性能的聚合物电催化剂系统提供了新的视角，从而促进 CO2RR 的应用。
{"title":"Promoting CO2 electroreduction activity of porphyrinic conjugated microporous polyanilines via accelerating proton transfer dynamics","authors":"Feng Qiu, Chunyan Li, Xiaodong Xuan, Senhe Huang, Chenbao Lu, Hualin Lin, Sheng Han, Xiao-Dong Zhuang, Wai-Yeung Raymond Wong","doi":"10.1039/d4ta05918b","DOIUrl":"https://doi.org/10.1039/d4ta05918b","url":null,"abstract":"Conjugated microporous polymers (CMPs) with π-conjugated framework, inherent porosity and tunable structure have been considered as the promising platforms as electrocatalysts for carbon dioxide reduction reaction (CO2RR). Promoting the proton transfer dynamic to modulate microenvironment of active sites in CMPs plays an important role on the improvement of their electrocatalytic activity. Herein, we developed a series of novel porphyrinic conjugated microporous polyanilines (CMPANI-n) constructed from tetrabromo-cobalt(II) porphyrin and diamino aromatics by the Buchwald–Hartwig coupling polymerization approach. Owing to the three-dimensional geometry of these polymeric skeleton, microenvironment of catalytic CoN4 site could be readily regulated by incorporation of nitrogen-doped diamino aromatic, leading to the enhancement of electrocatalytic activity for the carbon monoxide (CO) production. Notably, pyrazine-containing CMPANI (CMPANI-3) shows the high CO Faradaic efficiency (FECO) (97 % at −0.7 V vs. RHE), excellent turnover frequency (TOF) (2264 h−1 at −0.7 V vs. RHE) and large current density (>200 mA cm−2). The kinetic isotope effect results indicate that the pyrazinyl-N in CMPANI-3 facilitates the efficient proton absorption and transfer. Moreover, in-situ Fourier transform infrared spectra demonstrate that the protonated pyrazinyl-N would promote the generation and stabilization of *COOH intermediate via the coordination interaction around CoN4 site, thus favoring the electroreduction of CO2-to-CO conversion. This work provides a new sight in the design of polymeric electrocatalyst system with superior electron and proton transport for boosting CO2RR applications.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"3 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610093","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Designing high-performance, environmentally friendly, and durable bifunctional electrode materials for electrocatalytic water splitting is a key challenge in implementing sustainable energy technology. Here, we report a bionic modification of wood cell walls inspired by marine mussel adhesive proteins to develop a cost-effective yet high-efficiency wood-based bifunctional electrocatalyst. Ni–Co binary nanoparticles integrated with nitrogen-doped carbonized wood (Ni–Co/N@CW) were prepared by capitalizing on porous wood cell walls as confined spaces. Dopamine was adopted as an adhesive to achieve homogeneous dispersion of the nanoparticles, followed by forming graphitic carbon layers to encapsulate the nanoparticles through a calcination process. Structural and morphological studies revealed that the optimal Ni–Co/N@CW possesses a large surface area, abundant mesopores, and significant N doping in the carbonized wood framework, with 85% of pyridinic N. When employed as both the anode and cathode electrocatalyst in an alkaline medium, the cost-effective Ni–Co/N@CW catalyst manifests outstanding catalytic performance with low overpotentials and robust stability, surpassing the counterparts and recently reported earth-abundant electrocatalysts for both the oxygen evolution reaction (OER; overpotential of 290 mV at 10 mA cm−2) and hydrogen evolution reaction (HER; overpotential of 143 mV at 10 mA cm−2). Most notably, the as-prepared electrode achieves a current density of 10 mA cm−2 at a comparatively low voltage of 1.60 V during overall water splitting in an alkaline electrolyzer. The hierarchically porous structures, advanced mass and charge transport ability (attributed to pyridinic N and graphitic C), and abundant active centers (Ni–Co binary metal sites) collectively unveil a synergistic effect that enhances the water-splitting catalytic activity of Ni–Co/N@CW, as revealed by a series of characterization studies and density functional theory (DFT) calculations. Additionally, the remarkable structural and chemical stability of the hierarchically porous Ni–Co/N@CW results in the (–) Ni–Co/N@CW‖Ni–Co/N@CW (+) water electrolysis cell displaying excellent long-term stability. The development of efficient and economic-friendly self-supported electrodes could contribute to the related energy-conversion systems and advance the progress of biomass-based devices.
为电催化水分离设计高性能、环保、耐用的双功能电极材料是实现可持续能源技术的关键挑战。在此，我们报告了受海洋贻贝粘合蛋白的启发，对木材细胞壁进行仿生改造，从而开发出一种经济高效的木基双功能电催化剂。利用多孔的木材细胞壁作为密闭空间，制备了与掺氮碳化木材（Ni-Co/N@CW）结合在一起的镍钴二元纳米颗粒。采用多巴胺作为粘合剂实现纳米粒子的均匀分散，然后通过煅烧过程形成石墨碳层将纳米粒子包裹起来。结构和形态研究表明，最佳的 Ni-Co/N@CW 具有较大的比表面积、丰富的中孔，并且在碳化木框架中掺杂了大量的 N，其中 85% 为吡啶 N。当在碱性介质中同时用作阳极和阴极电催化剂时，这种具有成本效益的 Ni-Co/N@CW 催化剂表现出卓越的催化性能，过电位低且稳定性强，在氧进化反应（OER；10 mA cm-2 时过电位为 290 mV）和氢进化反应（HER；10 mA cm-2 时过电位为 143 mV）方面均超过了同类催化剂和最近报道的富土电催化剂。最值得注意的是，在碱性电解槽中进行整体水分离时，制备的电极在 1.60 V 的相对较低电压下就能达到 10 mA cm-2 的电流密度。通过一系列表征研究和密度泛函理论（DFT）计算，Ni-Co/N@CW 的多孔分层结构、先进的质量和电荷传输能力（归功于吡啶 N 和石墨 C）以及丰富的活性中心（Ni-Co 二元金属位点）共同揭示了一种协同效应，提高了 Ni-Co/N@CW 的水分离催化活性。此外，分层多孔 Ni-Co/N@CW 具有显著的结构和化学稳定性，使得 (-) Ni-Co/N@CW‖Ni-Co/N@CW (+) 水电解池显示出卓越的长期稳定性。开发高效、经济的自支撑电极有助于相关的能量转换系统，并推动生物质能设备的发展。
{"title":"Self-supported N-doped carbon-coupled Ni–Co binary nanoparticle electrodes derived from bionic design of wood cell walls for durable overall water splitting","authors":"Congcong Yang, Ruixi Jin, Zhihang Liu, Shilei Li, Dong Lv, Jingshuo Liu, Jian Li, Zhiqun Lin, Likun Gao","doi":"10.1039/d4ta06772j","DOIUrl":"https://doi.org/10.1039/d4ta06772j","url":null,"abstract":"Designing high-performance, environmentally friendly, and durable bifunctional electrode materials for electrocatalytic water splitting is a key challenge in implementing sustainable energy technology. Here, we report a bionic modification of wood cell walls inspired by marine mussel adhesive proteins to develop a cost-effective yet high-efficiency wood-based bifunctional electrocatalyst. Ni–Co binary nanoparticles integrated with nitrogen-doped carbonized wood (Ni–Co/N@CW) were prepared by capitalizing on porous wood cell walls as confined spaces. Dopamine was adopted as an adhesive to achieve homogeneous dispersion of the nanoparticles, followed by forming graphitic carbon layers to encapsulate the nanoparticles through a calcination process. Structural and morphological studies revealed that the optimal Ni–Co/N@CW possesses a large surface area, abundant mesopores, and significant N doping in the carbonized wood framework, with 85% of pyridinic N. When employed as both the anode and cathode electrocatalyst in an alkaline medium, the cost-effective Ni–Co/N@CW catalyst manifests outstanding catalytic performance with low overpotentials and robust stability, surpassing the counterparts and recently reported earth-abundant electrocatalysts for both the oxygen evolution reaction (OER; overpotential of 290 mV at 10 mA cm<small><sup>−2</sup></small>) and hydrogen evolution reaction (HER; overpotential of 143 mV at 10 mA cm<small><sup>−2</sup></small>). Most notably, the as-prepared electrode achieves a current density of 10 mA cm<small><sup>−2</sup></small> at a comparatively low voltage of 1.60 V during overall water splitting in an alkaline electrolyzer. The hierarchically porous structures, advanced mass and charge transport ability (attributed to pyridinic N and graphitic C), and abundant active centers (Ni–Co binary metal sites) collectively unveil a synergistic effect that enhances the water-splitting catalytic activity of Ni–Co/N@CW, as revealed by a series of characterization studies and density functional theory (DFT) calculations. Additionally, the remarkable structural and chemical stability of the hierarchically porous Ni–Co/N@CW results in the (–) Ni–Co/N@CW‖Ni–Co/N@CW (+) water electrolysis cell displaying excellent long-term stability. The development of efficient and economic-friendly self-supported electrodes could contribute to the related energy-conversion systems and advance the progress of biomass-based devices.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"804 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610167","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Faqiang Feng, Yufeng Yang, Qiuquan Yu, Dan Lei, Jinjie Ye, Kun Li, Bo Wang
<p>Severe vitamin E deficiency causes ataxia, neuropathy, anaemia and other health conditions, and inadequate vitamin E status is prevalent in healthy population (Malik <i>et al</i>., <span>2021</span>). Meanwhile, global food production falls short in delivering sufficient vitamin E, resulting in a nutrient gap of 31% (Smith <i>et al</i>., <span>2021</span>). Although various tocochromanol isoforms are found in crop seeds, only α-tocopherol exhibits the highest biological activity and liver tissue concentration (Traber, <span>2024</span>). However, crop tend to accumulate abundant γ-tocopherol and α-tocopherol content is lower than that of γ-tocopherol (Mène-Saffrané and Pellaud, <span>2017</span>). Therefore, exploring new genes to enhance α-tocopherol content and α/γ-tocopherol ratio in staple crop is attractive.</p> <p>As a globally significant staple crop, maize (<i>Zea mays</i> L.) provides abundant tocopherols for enhancing human health. The biosynthesis of α-tocopherol regulated by two key enzymes ZmVTE1 and ZmVTE4 in maize (Li <i>et al</i>., <span>2012</span>; Sattler <i>et al</i>., <span>2003</span>). In our previous study, we identified a quantitative trait locus (QTL) within the umc1177–bnlg1429 interval on chromosome 1 that contributes to the highest α/γ-tocopherol ratio (41.16%) in sweet corn (Feng <i>et al</i>., <span>2013</span>). <i>ZmSPS2</i> (<i>Zm00001d027694</i>, named according to the genome annotation ‘Solanesyl diphosphate synthase 2 chloroplastic’), located in this genomic region (Table S1), is co-expressed with vitamin E biosynthesis genes (<i>ZmVTE1</i> and <i>ZmVTE4</i>) (Tables S2, S3). Furthermore, the expression profile of <i>ZmSPS2</i> is consistent with changes in α/γ-tocopherol ratio during the kernel development (Figure 1a). In addition, three ZmSPS2 homologues with complete conserved domain were obtained in maize (Figure S1, Table S4). And the expression profile of these SPS2 homologues is not correlated with changes in α/γ-tocopherol ratio during the kernel development (Figure S2). These findings suggest the possibility of modulating α/γ-tocopherol ratio through <i>ZmSPS2</i>. In the present study, both maize mutants and overexpression lines were obtained; subsequently, the tocopherol contents compared to the wild-type plants were explored.</p> <figure><picture> <source media="(min-width: 1650px)" srcset="/cms/asset/d6bd057c-fe27-494e-ad93-e3b2dda09ada/pbi14516-fig-0001-m.jpg"/><img alt="Details are in the caption following the image" data-lg-src="/cms/asset/d6bd057c-fe27-494e-ad93-e3b2dda09ada/pbi14516-fig-0001-m.jpg" loading="lazy" src="/cms/asset/33034fae-8c3a-49d7-96fb-b2207ceb558a/pbi14516-fig-0001-m.png" title="Details are in the caption following the image"/></picture><figcaption> <div><strong>Figure 1<span style="font-weight:normal"></span></strong><div>Open in figure viewer<i aria-hidden="true"></i><span>PowerPoint</span></div> </div> <div>Overexpression <i>ZmSPS2</i> increases α-tocopherol accumulati
{"title":"Overexpression of ZmSPS2 increases α/γ-tocopherol ratio to improve maize nutritional quality","authors":"Faqiang Feng, Yufeng Yang, Qiuquan Yu, Dan Lei, Jinjie Ye, Kun Li, Bo Wang","doi":"10.1111/pbi.14516","DOIUrl":"https://doi.org/10.1111/pbi.14516","url":null,"abstract":"<p>Severe vitamin E deficiency causes ataxia, neuropathy, anaemia and other health conditions, and inadequate vitamin E status is prevalent in healthy population (Malik <i>et al</i>., <span>2021</span>). Meanwhile, global food production falls short in delivering sufficient vitamin E, resulting in a nutrient gap of 31% (Smith <i>et al</i>., <span>2021</span>). Although various tocochromanol isoforms are found in crop seeds, only α-tocopherol exhibits the highest biological activity and liver tissue concentration (Traber, <span>2024</span>). However, crop tend to accumulate abundant γ-tocopherol and α-tocopherol content is lower than that of γ-tocopherol (Mène-Saffrané and Pellaud, <span>2017</span>). Therefore, exploring new genes to enhance α-tocopherol content and α/γ-tocopherol ratio in staple crop is attractive.</p>\u0000<p>As a globally significant staple crop, maize (<i>Zea mays</i> L.) provides abundant tocopherols for enhancing human health. The biosynthesis of α-tocopherol regulated by two key enzymes ZmVTE1 and ZmVTE4 in maize (Li <i>et al</i>., <span>2012</span>; Sattler <i>et al</i>., <span>2003</span>). In our previous study, we identified a quantitative trait locus (QTL) within the umc1177–bnlg1429 interval on chromosome 1 that contributes to the highest α/γ-tocopherol ratio (41.16%) in sweet corn (Feng <i>et al</i>., <span>2013</span>). <i>ZmSPS2</i> (<i>Zm00001d027694</i>, named according to the genome annotation ‘Solanesyl diphosphate synthase 2 chloroplastic’), located in this genomic region (Table S1), is co-expressed with vitamin E biosynthesis genes (<i>ZmVTE1</i> and <i>ZmVTE4</i>) (Tables S2, S3). Furthermore, the expression profile of <i>ZmSPS2</i> is consistent with changes in α/γ-tocopherol ratio during the kernel development (Figure 1a). In addition, three ZmSPS2 homologues with complete conserved domain were obtained in maize (Figure S1, Table S4). And the expression profile of these SPS2 homologues is not correlated with changes in α/γ-tocopherol ratio during the kernel development (Figure S2). These findings suggest the possibility of modulating α/γ-tocopherol ratio through <i>ZmSPS2</i>. In the present study, both maize mutants and overexpression lines were obtained; subsequently, the tocopherol contents compared to the wild-type plants were explored.</p>\u0000<figure><picture>\u0000<source media=\"(min-width: 1650px)\" srcset=\"/cms/asset/d6bd057c-fe27-494e-ad93-e3b2dda09ada/pbi14516-fig-0001-m.jpg\"/><img alt=\"Details are in the caption following the image\" data-lg-src=\"/cms/asset/d6bd057c-fe27-494e-ad93-e3b2dda09ada/pbi14516-fig-0001-m.jpg\" loading=\"lazy\" src=\"/cms/asset/33034fae-8c3a-49d7-96fb-b2207ceb558a/pbi14516-fig-0001-m.png\" title=\"Details are in the caption following the image\"/></picture><figcaption>\u0000<div><strong>Figure 1<span style=\"font-weight:normal\"></span></strong><div>Open in figure viewer<i aria-hidden=\"true\"></i><span>PowerPoint</span></div>\u0000</div>\u0000<div>Overexpression <i>ZmSPS2</i> increases α-tocopherol accumulati","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"153 1","pages":""},"PeriodicalIF":13.8,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601435","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mohsen Tamtaji, William A. Goddard III, Guanhua Chen
Metal complexes have been thoroughly investigated for a wide range of electrochemical reactions. However, mechanically interlocked molecular machines (MIM) have not been investigated for electrochemistry through a systematic high throughput screening. Here we introduce the concept of MIM Catenane metal complexes with a dynamic coordination environment around the metal center aimed towards enhanced CO2 reduction reaction (CO2RR), hydrogen evolution reaction (HER), oxygen reduction reaction (ORR), and/or oxygen evolution reaction (OER). We applied density functional theory (DFT) to screen 3d transition metals supported by Catenane metal complexes denoted as M(II)CN6 and Co(I)CNX=4, 5, or 6. We found that among all the 3d transition metals, only monovalent Co(I) is suitable as an application as a molecular machine. We sought catalysts with high thermodynamic and electrochemical stabilities along with low CO2RR, ORR, OER, and HER overpotentials. We find that HER takes place on neighboring nitrogen atoms of Cu(II)CN6 with an overpotential of 0.27 V. Moreover, CO2RR, ORR, and OER take place on the metal active sites of Ti(II)CN6, Cr(II)CN6, and Co(II)CN6, with overpotentials of 1.12 V, 0.36 V, and 0.81 V, respectively. This paper provides fundamental insights into the design of advanced MIM catalysts by applying the concept of a dynamic coordination environment for electrochemistry at room temperature.
人们已经深入研究了金属复合物在多种电化学反应中的应用。然而，人们还没有通过系统的高通量筛选研究过用于电化学反应的机械互锁分子机器（MIM）。在此，我们引入了 MIM 卡特烷金属配合物的概念，该配合物的金属中心周围具有动态配位环境，旨在增强二氧化碳还原反应（CO2RR）、氢进化反应（HER）、氧还原反应（ORR）和/或氧进化反应（OER）。我们应用密度泛函理论（DFT）筛选了由卡滕烷金属配合物（M(II)CN6 和 Co(I)CNX=4, 5 或 6）支持的 3d 过渡金属。我们发现，在所有 3d 过渡金属中，只有一价 Co(I) 适合用作分子机器。我们寻求热力学和电化学稳定性高且 CO2RR、ORR、OER 和 HER 过电位低的催化剂。我们发现，HER 发生在 Cu(II)CN6 的邻近氮原子上，过电势为 0.27 V。此外，CO2RR、ORR 和 OER 发生在 Ti(II)CN6、Cr(II)CN6 和 Co(II)CN6 的金属活性位点上，过电势分别为 1.12 V、0.36 V 和 0.81 V。本文通过应用室温电化学动态配位环境的概念，为设计先进的 MIM 催化剂提供了基本见解。
{"title":"High-throughput Screening of Mechanically Interlocked Catenane Metal Complexes for Enhanced Electrocatalytic Activity","authors":"Mohsen Tamtaji, William A. Goddard III, Guanhua Chen","doi":"10.1039/d4ta06497f","DOIUrl":"https://doi.org/10.1039/d4ta06497f","url":null,"abstract":"Metal complexes have been thoroughly investigated for a wide range of electrochemical reactions. However, mechanically interlocked molecular machines (MIM) have not been investigated for electrochemistry through a systematic high throughput screening. Here we introduce the concept of MIM Catenane metal complexes with a dynamic coordination environment around the metal center aimed towards enhanced CO2 reduction reaction (CO2RR), hydrogen evolution reaction (HER), oxygen reduction reaction (ORR), and/or oxygen evolution reaction (OER). We applied density functional theory (DFT) to screen 3d transition metals supported by Catenane metal complexes denoted as M(II)CN6 and Co(I)CNX=4, 5, or 6. We found that among all the 3d transition metals, only monovalent Co(I) is suitable as an application as a molecular machine. We sought catalysts with high thermodynamic and electrochemical stabilities along with low CO2RR, ORR, OER, and HER overpotentials. We find that HER takes place on neighboring nitrogen atoms of Cu(II)CN6 with an overpotential of 0.27 V. Moreover, CO2RR, ORR, and OER take place on the metal active sites of Ti(II)CN6, Cr(II)CN6, and Co(II)CN6, with overpotentials of 1.12 V, 0.36 V, and 0.81 V, respectively. This paper provides fundamental insights into the design of advanced MIM catalysts by applying the concept of a dynamic coordination environment for electrochemistry at room temperature.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"80 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601812","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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