Carbon-based adsorbents have been recently identified as advanced materials for the efficient removal of perfluorooctanoic acid (PFOA); however, the fundamental understanding of the selective adsorption of PFOA over competing contaminants/water matrix is still lacking. Herein, a novel honeycomb-like nitrogen-doped carbon nanosheet (HL-NC@Ni-800) material was reported for the rapid adsorption of PFOA. The PFOA selective adsorption was attributed to (i) favorable steric hindrance that allowed rapid and stable PFOA adsorption, (ii) abundant adsorption sites provided by the honeycomb-like mesoporous structure, (iii) electrostatic attraction between the PFOA anion and nickel cation, (iv) hydrophobic effect between the PFOA tail and nitrogen functional groups, and (v) Lewis acid–base effect. Consequently, PFOA was efficiently removed from the competing contaminants such as 1,4-dioxane and sulfamethoxazole by 94.6 and 89.6%, respectively, as well as the water matrix such as inorganic anions by ∼84–94% and real high-salinity seawater by 75.6–78.4%. The calculated maximum adsorption capacities (qm) of HL-NC@Ni-800 for PFOA soared to 184.89 mg·g–1. In addition, the thermodynamically favorable adsorption of PFOA with different steric conformations on HL-NC@Ni-800 provided theoretical explanations for its high-efficiency adsorption performance toward PFOA. This study provides a novel strategy for the synthesis method of efficient adsorbents for PFOA and also elucidates the mechanistic understandings of PFOA selective adsorption over competing contaminants/water matrix, for guiding the design of more efficient adsorbents to treat PFOA-contaminated water.
{"title":"Fast Perfluorooctanoic Acid (PFOA) Removal with Honeycomb-like Nitrogen-Doped Carbon Nanosheets: Mechanisms for the Selective Adsorption of PFOA over Competing Contaminants/Water Matrix","authors":"Lingyu Chen, Kuanchang He, Wei Li, Dongmei Ma, Xiaodong Xin, Gang Wang, Qian Liu, Lihui Yang, Faliang Cheng, Sihao Lv, Defeng Xing","doi":"10.1021/acsestengg.4c00418","DOIUrl":"https://doi.org/10.1021/acsestengg.4c00418","url":null,"abstract":"Carbon-based adsorbents have been recently identified as advanced materials for the efficient removal of perfluorooctanoic acid (PFOA); however, the fundamental understanding of the selective adsorption of PFOA over competing contaminants/water matrix is still lacking. Herein, a novel honeycomb-like nitrogen-doped carbon nanosheet (HL-NC@Ni-800) material was reported for the rapid adsorption of PFOA. The PFOA selective adsorption was attributed to (i) favorable steric hindrance that allowed rapid and stable PFOA adsorption, (ii) abundant adsorption sites provided by the honeycomb-like mesoporous structure, (iii) electrostatic attraction between the PFOA anion and nickel cation, (iv) hydrophobic effect between the PFOA tail and nitrogen functional groups, and (v) Lewis acid–base effect. Consequently, PFOA was efficiently removed from the competing contaminants such as 1,4-dioxane and sulfamethoxazole by 94.6 and 89.6%, respectively, as well as the water matrix such as inorganic anions by ∼84–94% and real high-salinity seawater by 75.6–78.4%. The calculated maximum adsorption capacities (<i>q</i><sub>m</sub>) of HL-NC@Ni-800 for PFOA soared to 184.89 mg·g<sup>–1</sup>. In addition, the thermodynamically favorable adsorption of PFOA with different steric conformations on HL-NC@Ni-800 provided theoretical explanations for its high-efficiency adsorption performance toward PFOA. This study provides a novel strategy for the synthesis method of efficient adsorbents for PFOA and also elucidates the mechanistic understandings of PFOA selective adsorption over competing contaminants/water matrix, for guiding the design of more efficient adsorbents to treat PFOA-contaminated water.","PeriodicalId":7008,"journal":{"name":"ACS ES&T engineering","volume":"44 1","pages":""},"PeriodicalIF":7.1,"publicationDate":"2024-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142204235","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
To improve the water resistance of manganese oxide (MnOx) in the catalytic ozonation of dimethyl sulfide (DMS) under humid conditions, polymorphic MnOx was synthesized based on δ-MnO2 with reference to the in situ layer-to-tunnel (L–T) transition of minerals in a natural environment. The constructed polymorphic MnOx(Mn–SH) possessed abundant α–δ (α(Mn)-O-δ(Mn)) interfaces and exhibited superior catalytic activity for the conversion of DMS, ensuring more than 91% of DMS removal under harsh conditions [relative humidity (RH) = 80%] and excellent stability after testing for 20 h (RH = 60–80%). In situ DRIFTS spectra and theoretical calculations demonstrated that α–δ interfaces facilitated the formation of active hydroxyl groups (−OH) through H2O dissociation, which can participate in ozone (O3) activation and avoid the deactivation caused by H2O. Simultaneously, more Brønsted acid sites formed through H2O dissociation, which promoted DMS adsorption and decomposition. This study gives an understanding of the role of α–δ interfaces in promoting activity for catalytic ozonation and provides a convenient strategy to construct polymorphic MnOx with enhanced water resistance, which can be applied to existing MnOx used for catalytic ozonation of sulfur-containing compounds from livestock farms and the petroleum industries.
{"title":"Flower-like Polymorphic MnOx Constructed by In Situ L–T Transition with Superior Performance in the Catalytic Ozonation of Dimethyl Sulfide under Humid Conditions","authors":"Feiyang He, Wenji Feng, Xinru Chen, Yunshuo Wu, Haiqiang Wang, Zhongbiao Wu","doi":"10.1021/acsestengg.4c00404","DOIUrl":"https://doi.org/10.1021/acsestengg.4c00404","url":null,"abstract":"To improve the water resistance of manganese oxide (MnO<sub><i>x</i></sub>) in the catalytic ozonation of dimethyl sulfide (DMS) under humid conditions, polymorphic MnO<sub><i>x</i></sub> was synthesized based on δ-MnO<sub>2</sub> with reference to the in situ layer-to-tunnel (L–T) transition of minerals in a natural environment. The constructed polymorphic MnO<sub><i>x</i></sub>(Mn–SH) possessed abundant α–δ (α(Mn)-O-δ(Mn)) interfaces and exhibited superior catalytic activity for the conversion of DMS, ensuring more than 91% of DMS removal under harsh conditions [relative humidity (RH) = 80%] and excellent stability after testing for 20 h (RH = 60–80%). In situ DRIFTS spectra and theoretical calculations demonstrated that α–δ interfaces facilitated the formation of active hydroxyl groups (−OH) through H<sub>2</sub>O dissociation, which can participate in ozone (O<sub>3</sub>) activation and avoid the deactivation caused by H<sub>2</sub>O. Simultaneously, more Brønsted acid sites formed through H<sub>2</sub>O dissociation, which promoted DMS adsorption and decomposition. This study gives an understanding of the role of α–δ interfaces in promoting activity for catalytic ozonation and provides a convenient strategy to construct polymorphic MnO<sub><i>x</i></sub> with enhanced water resistance, which can be applied to existing MnO<sub><i>x</i></sub> used for catalytic ozonation of sulfur-containing compounds from livestock farms and the petroleum industries.","PeriodicalId":7008,"journal":{"name":"ACS ES&T engineering","volume":"403 1","pages":""},"PeriodicalIF":7.1,"publicationDate":"2024-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142204229","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Anaerobic granular sludge (AnGS) is valuable for the treatment of high concentration organic wastewater but is hampered from further development by poor stability. Quorum sensing (QS) has been shown as an effective strategy to enhance the stability of AnGS, whereas the long-term resistance and underlying mechanisms remain uncertain. This work investigates the reinforcing effect of the QS on AnGS and the internal regulation mechanisms. The chemical oxygen demand (COD) removal was maintained at preshock level (90–93%) after multiple temperature shocks in the N-acyl-homoserine lactones (AHLs)-induced system. AHLs-mediated QS led to an increase in gene abundance of the four hydrophobic amino acids with protein (PN) increasing by 33.1%, which optimized the construction of the protective barrier of extracellular polymeric substances (EPS). AHLs also reshaped the functional microbial community and enhanced metabolic activities, promoting both the hydrogenotrophic and methanotrophic methanogenic pathways. In addition, the abundance of Geobacter and Methanothrix was increased by 4.4% and 2.3% under the stimulation of exogenous AHLs, which enhanced the direct interspecies electron transfer (DIET) pathway. This study provides a strategy for enhancing the stability of AnGS in the face of environmental shocks and gives a comprehensive theoretical foundation for exogenous AHLs-mediated QS regulation of anaerobic biological treatment.
{"title":"New Insights into the Persistent Shock Resistance of Anaerobic Granular Sludge Based on Quorum Sensing Regulation: A Novel Gene Regulatory Mechanism","authors":"Longyi Lv, Ziyin Wei, Chendi Feng, Jiarui Chen, Weiguang Li, Jiyong Bian, Zhijun Ren, Guangming Zhang","doi":"10.1021/acsestengg.4c00334","DOIUrl":"https://doi.org/10.1021/acsestengg.4c00334","url":null,"abstract":"Anaerobic granular sludge (AnGS) is valuable for the treatment of high concentration organic wastewater but is hampered from further development by poor stability. Quorum sensing (QS) has been shown as an effective strategy to enhance the stability of AnGS, whereas the long-term resistance and underlying mechanisms remain uncertain. This work investigates the reinforcing effect of the QS on AnGS and the internal regulation mechanisms. The chemical oxygen demand (COD) removal was maintained at preshock level (90–93%) after multiple temperature shocks in the <i>N</i>-acyl-homoserine lactones (AHLs)-induced system. AHLs-mediated QS led to an increase in gene abundance of the four hydrophobic amino acids with protein (PN) increasing by 33.1%, which optimized the construction of the protective barrier of extracellular polymeric substances (EPS). AHLs also reshaped the functional microbial community and enhanced metabolic activities, promoting both the hydrogenotrophic and methanotrophic methanogenic pathways. In addition, the abundance of <i>Geobacter</i> and <i>Methanothrix</i> was increased by 4.4% and 2.3% under the stimulation of exogenous AHLs, which enhanced the direct interspecies electron transfer (DIET) pathway. This study provides a strategy for enhancing the stability of AnGS in the face of environmental shocks and gives a comprehensive theoretical foundation for exogenous AHLs-mediated QS regulation of anaerobic biological treatment.","PeriodicalId":7008,"journal":{"name":"ACS ES&T engineering","volume":"5 1","pages":""},"PeriodicalIF":7.1,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142204230","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-03DOI: 10.1021/acsestengg.4c00453
Duoduo Fang, Di Luo, Han Xiao, Jiaxing Li, Lin Ma, Jiangzhi Zi, Zichao Lian
Achieving high effective degradation of organic pollutants in sewage having adverse effects on human health and ecosystems remains a major challenge. In this study, an oxygen vacancy (Ov)-mediated Z-scheme Co3O4/Ov-TiO2 heterojunction was first reported for simultaneous selective photoelectrocatalytic pollutant degradation and hydrogen production under visible light irradiation. The optimized Co3O4/Ov-TiO2 exhibited excellent photoelectrocatalytic performance in the degradation of the organic pollutants under visible light irradiation due to the formation of a Z-scheme heterojunction for the utilization of highly reductive photogenerated electrons and oxidative holes. The mechanistic investigation suggested that the synergistic effects of hydroxyl radical and singlet oxygen as the dominant reactive species facilitated the ring-open reactions of the rhodamine B for the mineralization processes. This work provides a deep understanding of designing Z-scheme heterojunction photoelectrocatalysts through defect engineering technologies for sewage treatment.
如何高效降解污水中对人类健康和生态系统产生不利影响的有机污染物仍然是一项重大挑战。本研究首次报道了一种由氧空位（Ov）介导的 Z 型 Co3O4/Ov-TiO2 异质结，可在可见光照射下同时进行选择性光电催化污染物降解和制氢。优化后的 Co3O4/Ov-TiO2 在可见光照射下降解有机污染物时表现出优异的光电催化性能，这是由于形成的 Z 型异质结利用了高还原性光生电子和氧化空穴。机理研究表明，羟基自由基和单线态氧作为主要活性物种的协同效应促进了罗丹明 B 的开环反应，从而实现矿化过程。这项工作为通过缺陷工程技术设计 Z 型异质结光电催化剂以用于污水处理提供了深入的理解。
{"title":"Oxygen Vacancies-Mediated Z-Scheme Mechanism Promotes Synergistic Photoelectrocatalysis for Hydroxyl Radical and Singlet Oxygen-Cooperating on Selective Pollutant Degradation","authors":"Duoduo Fang, Di Luo, Han Xiao, Jiaxing Li, Lin Ma, Jiangzhi Zi, Zichao Lian","doi":"10.1021/acsestengg.4c00453","DOIUrl":"https://doi.org/10.1021/acsestengg.4c00453","url":null,"abstract":"Achieving high effective degradation of organic pollutants in sewage having adverse effects on human health and ecosystems remains a major challenge. In this study, an oxygen vacancy (O<sub>v</sub>)-mediated Z-scheme Co<sub>3</sub>O<sub>4</sub>/O<sub>v</sub>-TiO<sub>2</sub> heterojunction was first reported for simultaneous selective photoelectrocatalytic pollutant degradation and hydrogen production under visible light irradiation. The optimized Co<sub>3</sub>O<sub>4</sub>/O<sub>v</sub>-TiO<sub>2</sub> exhibited excellent photoelectrocatalytic performance in the degradation of the organic pollutants under visible light irradiation due to the formation of a Z-scheme heterojunction for the utilization of highly reductive photogenerated electrons and oxidative holes. The mechanistic investigation suggested that the synergistic effects of hydroxyl radical and singlet oxygen as the dominant reactive species facilitated the ring-open reactions of the rhodamine B for the mineralization processes. This work provides a deep understanding of designing Z-scheme heterojunction photoelectrocatalysts through defect engineering technologies for sewage treatment.","PeriodicalId":7008,"journal":{"name":"ACS ES&T engineering","volume":"14 1","pages":""},"PeriodicalIF":7.1,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142204231","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-30DOI: 10.1021/acsestengg.4c00400
Yi Shen, Mingzheng Yang, Chao Zhu, Haizhong Zhang, Renlan Liu, Jun Wang, Qile Fang, Shuang Song, Baoliang Chen
The activation of peroxymonosulfate (PMS) to generate singlet oxygen (1O2) for the removal of emerging organic pollutants (EOPs) from complex aqueous environments has garnered widespread attention. However, the low efficiency and selectivity of current PMS activation for 1O2 generation result in suboptimal EOP degradation. To enhance the selectivity of PMS activation and promote the non-radical pathway, non-metal heteroatoms with varying electronegativities were introduced to disrupt the symmetrical coordination structure of Fe active sites in Fe single-atom catalysts. The results showed that, in the B-Fe1/GLCNs/PMS system, the pseudo-first-order kinetic rate for bisphenol A (BPA) degradation reached 4.435 min–1, which is 7.4 times higher than that of the unmodified control group. Experimental and theoretical calculations demonstrated that the doping of non-metal heteroatoms altered the electron density and distribution at the Fe active sites, thereby modulating the adsorption configuration of HSO5– and increasing the selectivity for PMS activation to generate 1O2. Additionally, the degradation of EOPs by 1O2 produced intermediate products with lower biological toxicity, and 1O2 demonstrated strong anti-interference capability. The change in HSO5– morphology improved the rate of 1O2 generation. This study provides deep insights into designing high-performance PMS activation catalysts via non-metal doping to regulate the electronic structure of active sites for a selective non-radical pathway.
{"title":"Enhanced Selectivity in PMS Activation via Non-Metal Doping for Efficient 1O2 Generation in Emerging Organic Pollutants Degradation","authors":"Yi Shen, Mingzheng Yang, Chao Zhu, Haizhong Zhang, Renlan Liu, Jun Wang, Qile Fang, Shuang Song, Baoliang Chen","doi":"10.1021/acsestengg.4c00400","DOIUrl":"https://doi.org/10.1021/acsestengg.4c00400","url":null,"abstract":"The activation of peroxymonosulfate (PMS) to generate singlet oxygen (<sup>1</sup>O<sub>2</sub>) for the removal of emerging organic pollutants (EOPs) from complex aqueous environments has garnered widespread attention. However, the low efficiency and selectivity of current PMS activation for <sup>1</sup>O<sub>2</sub> generation result in suboptimal EOP degradation. To enhance the selectivity of PMS activation and promote the non-radical pathway, non-metal heteroatoms with varying electronegativities were introduced to disrupt the symmetrical coordination structure of Fe active sites in Fe single-atom catalysts. The results showed that, in the B-Fe<sub>1</sub>/GLCNs/PMS system, the pseudo-first-order kinetic rate for bisphenol A (BPA) degradation reached 4.435 min<sup>–1</sup>, which is 7.4 times higher than that of the unmodified control group. Experimental and theoretical calculations demonstrated that the doping of non-metal heteroatoms altered the electron density and distribution at the Fe active sites, thereby modulating the adsorption configuration of HSO<sub>5</sub><sup>–</sup> and increasing the selectivity for PMS activation to generate <sup>1</sup>O<sub>2</sub>. Additionally, the degradation of EOPs by <sup>1</sup>O<sub>2</sub> produced intermediate products with lower biological toxicity, and <sup>1</sup>O<sub>2</sub> demonstrated strong anti-interference capability. The change in HSO<sub>5</sub><sup>–</sup> morphology improved the rate of <sup>1</sup>O<sub>2</sub> generation. This study provides deep insights into designing high-performance PMS activation catalysts via non-metal doping to regulate the electronic structure of active sites for a selective non-radical pathway.","PeriodicalId":7008,"journal":{"name":"ACS ES&T engineering","volume":"18 1","pages":""},"PeriodicalIF":7.1,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142204233","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-30DOI: 10.1021/acsestengg.4c00308
Bo Cao, Yuxuan Zang, Beizhen Xie, Ting Zhao, Hongyu Zhao, Yanhong Ge, Hong Liu, Yue Yi
Electrochemically active bacteria (EAB) are catalysts of microbial electrogenesis and electrosynthesis, showing great prospects in wastewater treatment and biochemical engineering. However, isolating EAB is difficult, and only a few pure-cultured EAB have been reported. In this study, a novel gelled electrode based on an electrochemical plate is established, which for the first time realizes the selective screening of EAB strains and visible colony formation. A new EAB, Rhodococcus qingshengii C6, is isolated by using the method. R. qingshengii C6 is capable of electricity generation with a wide range of substrate spectra and is capable of reducing common electron acceptors by consuming electricity. The bidirectional extracellular electron transfer mechanism is preliminarily investigated, and exogenous redox mediators play an important role in extracellular electron transfer. This study provides an easy and simple method for the isolation and purification of EAB, contributing to the valuable bacterial resources exploration.
{"title":"Visualization Isolation of Electrochemically Active Bacteria by Using a Gelled Electrode-Based Electrochemical Plate","authors":"Bo Cao, Yuxuan Zang, Beizhen Xie, Ting Zhao, Hongyu Zhao, Yanhong Ge, Hong Liu, Yue Yi","doi":"10.1021/acsestengg.4c00308","DOIUrl":"https://doi.org/10.1021/acsestengg.4c00308","url":null,"abstract":"Electrochemically active bacteria (EAB) are catalysts of microbial electrogenesis and electrosynthesis, showing great prospects in wastewater treatment and biochemical engineering. However, isolating EAB is difficult, and only a few pure-cultured EAB have been reported. In this study, a novel gelled electrode based on an electrochemical plate is established, which for the first time realizes the selective screening of EAB strains and visible colony formation. A new EAB, <i>Rhodococcus qingshengii</i> C6, is isolated by using the method. <i>R. qingshengii</i> C6 is capable of electricity generation with a wide range of substrate spectra and is capable of reducing common electron acceptors by consuming electricity. The bidirectional extracellular electron transfer mechanism is preliminarily investigated, and exogenous redox mediators play an important role in extracellular electron transfer. This study provides an easy and simple method for the isolation and purification of EAB, contributing to the valuable bacterial resources exploration.","PeriodicalId":7008,"journal":{"name":"ACS ES&T engineering","volume":"37 1","pages":""},"PeriodicalIF":7.1,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142204232","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Palladium-zeolites are active catalysts for abating methane (CH4), the second largest greenhouse gas contributing to climate change, via catalytic combustion. Yet, it remains challenging to improve the activity of Pd-zeolites in CH4 combustion, in particular under humid conditions. Here, using small-pore SSZ-13 zeolite as a showcase, we demonstrate mesoporosity engineering as an effective approach to boost the CH4 combustion performance of Pd-zeolites. A newly designed gemini quaternary ammonium surfactant, namely C18–4N2MP, was fabricated using inexpensive reagents and employed as a mesoporogen in the hydrothermal synthesis of hierarchically micro–meso–macro–porous SSZ-13 product. High-dispersion Pd catalysts were achieved by using the hierarchically porous SSZ-13 zeolites as supports. Physicochemical characterization and reaction kinetics disclosed that rational mesoporosity engineering of the hierarchically porous SSZ-13, simply by optimizing C18–4N2MP addition in the precursor gel prior to hydrothermal crystallization, favored the formation of highly dispersed PdOx active phase and, in turn, the CH4 combustion without noticeable accumulation of carbonaceous intermediates on the surface. Additionally, mesoporosity-optimized Pd/SSZ-13 displayed improved durability and outstanding moisture resistance during CH4 combustion. This study sheds new light on the fabrication of high-performance Pd-zeolite catalysts for CH4 emission abatement by facile engineering of zeolite mesoporosity.
{"title":"Catalytic Methane Mitigation Over Mesoporosity-Engineered Hierarchically Porous Pd/SSZ-13 Zeolites","authors":"Gaozhou Liang, Anqi Guo, Wuwan Xiong, Dongdong Chen, Ulrich Simon, Daiqi Ye, Haibao Huang, Peirong Chen","doi":"10.1021/acsestengg.4c00347","DOIUrl":"https://doi.org/10.1021/acsestengg.4c00347","url":null,"abstract":"Palladium-zeolites are active catalysts for abating methane (CH<sub>4</sub>), the second largest greenhouse gas contributing to climate change, via catalytic combustion. Yet, it remains challenging to improve the activity of Pd-zeolites in CH<sub>4</sub> combustion, in particular under humid conditions. Here, using small-pore SSZ-13 zeolite as a showcase, we demonstrate mesoporosity engineering as an effective approach to boost the CH<sub>4</sub> combustion performance of Pd-zeolites. A newly designed gemini quaternary ammonium surfactant, namely C<sub>18–4</sub>N<sub>2</sub>MP, was fabricated using inexpensive reagents and employed as a mesoporogen in the hydrothermal synthesis of hierarchically micro–meso–macro–porous SSZ-13 product. High-dispersion Pd catalysts were achieved by using the hierarchically porous SSZ-13 zeolites as supports. Physicochemical characterization and reaction kinetics disclosed that rational mesoporosity engineering of the hierarchically porous SSZ-13, simply by optimizing C<sub>18–4</sub>N<sub>2</sub>MP addition in the precursor gel prior to hydrothermal crystallization, favored the formation of highly dispersed PdO<i><sub>x</sub></i> active phase and, in turn, the CH<sub>4</sub> combustion without noticeable accumulation of carbonaceous intermediates on the surface. Additionally, mesoporosity-optimized Pd/SSZ-13 displayed improved durability and outstanding moisture resistance during CH<sub>4</sub> combustion. This study sheds new light on the fabrication of high-performance Pd-zeolite catalysts for CH<sub>4</sub> emission abatement by facile engineering of zeolite mesoporosity.","PeriodicalId":7008,"journal":{"name":"ACS ES&T engineering","volume":"452 1","pages":""},"PeriodicalIF":7.1,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142226150","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Manganese-based materials are widely applied as catalysts for catalytic removal of gaseous pollutants due to their low cost and excellent redox performance. However, existing challenges such as unsatisfactory activity and stability hinder the application of manganese-based catalysts. Confining manganese-based materials into specific regions has the potential to influence intermolecular arrangement and mass diffusion and lower the activation energy barrier, thereby enhancing reaction stability and the catalyst’s activity. In this critical review, we briefly summarize the common reported nanoconfined manganese-based analogues for gaseous pollutant elimination including nitrogen oxides (NOx) and volatile organic compounds (VOCs). Details of the commonly reported hosts for confined catalysts and their impact on catalytic behavior and an in-depth discussion of the related mechanism are included. Through this critical review, we aim to raise the research attention on using confined catalysis as a fundamental guide or even tool to improve the catalytic performance of gaseous pollutant elimination.
{"title":"Confined Manganese-Based Catalysts for Gaseous Pollutant Removal: A Critical Review","authors":"Jialin Li, Zhijian Xiao, Jingling Yang, Mingshan Zhu","doi":"10.1021/acsestengg.4c00355","DOIUrl":"https://doi.org/10.1021/acsestengg.4c00355","url":null,"abstract":"Manganese-based materials are widely applied as catalysts for catalytic removal of gaseous pollutants due to their low cost and excellent redox performance. However, existing challenges such as unsatisfactory activity and stability hinder the application of manganese-based catalysts. Confining manganese-based materials into specific regions has the potential to influence intermolecular arrangement and mass diffusion and lower the activation energy barrier, thereby enhancing reaction stability and the catalyst’s activity. In this critical review, we briefly summarize the common reported nanoconfined manganese-based analogues for gaseous pollutant elimination including nitrogen oxides (NO<sub><i>x</i></sub>) and volatile organic compounds (VOCs). Details of the commonly reported hosts for confined catalysts and their impact on catalytic behavior and an in-depth discussion of the related mechanism are included. Through this critical review, we aim to raise the research attention on using confined catalysis as a fundamental guide or even tool to improve the catalytic performance of gaseous pollutant elimination.","PeriodicalId":7008,"journal":{"name":"ACS ES&T engineering","volume":"61 1","pages":""},"PeriodicalIF":7.1,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142226153","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-28DOI: 10.1021/acsestengg.4c0035510.1021/acsestengg.4c00355
Jialin Li, Zhijian Xiao, Jingling Yang* and Mingshan Zhu*,
Manganese-based materials are widely applied as catalysts for catalytic removal of gaseous pollutants due to their low cost and excellent redox performance. However, existing challenges such as unsatisfactory activity and stability hinder the application of manganese-based catalysts. Confining manganese-based materials into specific regions has the potential to influence intermolecular arrangement and mass diffusion and lower the activation energy barrier, thereby enhancing reaction stability and the catalyst’s activity. In this critical review, we briefly summarize the common reported nanoconfined manganese-based analogues for gaseous pollutant elimination including nitrogen oxides (NOx) and volatile organic compounds (VOCs). Details of the commonly reported hosts for confined catalysts and their impact on catalytic behavior and an in-depth discussion of the related mechanism are included. Through this critical review, we aim to raise the research attention on using confined catalysis as a fundamental guide or even tool to improve the catalytic performance of gaseous pollutant elimination.
{"title":"Confined Manganese-Based Catalysts for Gaseous Pollutant Removal: A Critical Review","authors":"Jialin Li, Zhijian Xiao, Jingling Yang* and Mingshan Zhu*, ","doi":"10.1021/acsestengg.4c0035510.1021/acsestengg.4c00355","DOIUrl":"https://doi.org/10.1021/acsestengg.4c00355https://doi.org/10.1021/acsestengg.4c00355","url":null,"abstract":"<p >Manganese-based materials are widely applied as catalysts for catalytic removal of gaseous pollutants due to their low cost and excellent redox performance. However, existing challenges such as unsatisfactory activity and stability hinder the application of manganese-based catalysts. Confining manganese-based materials into specific regions has the potential to influence intermolecular arrangement and mass diffusion and lower the activation energy barrier, thereby enhancing reaction stability and the catalyst’s activity. In this critical review, we briefly summarize the common reported nanoconfined manganese-based analogues for gaseous pollutant elimination including nitrogen oxides (NO<sub><i>x</i></sub>) and volatile organic compounds (VOCs). Details of the commonly reported hosts for confined catalysts and their impact on catalytic behavior and an in-depth discussion of the related mechanism are included. Through this critical review, we aim to raise the research attention on using confined catalysis as a fundamental guide or even tool to improve the catalytic performance of gaseous pollutant elimination.</p>","PeriodicalId":7008,"journal":{"name":"ACS ES&T engineering","volume":"4 9","pages":"2078–2096 2078–2096"},"PeriodicalIF":7.4,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142228402","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-27DOI: 10.1021/acsestengg.4c00325
Chongchong Qi, Tao Hu, Mengting Wu, Yong Sik Ok, Han Wang, Liyuan Chai, Zhang Lin
Accurate and large-scale estimation of the soil adsorption capacity of heavy metals (HMs) is vital to tackle soil HM contamination. Here, a novel framework has been developed to evaluate the adsorption capacity of HMs in soil using visible and near-infrared spectroscopy. Soil attributes were accurately estimated without any spectral preprocessing using a combined autoencoder (AE) and deep neural network (DNN) approach. Soil HM adsorption capability was then evaluated based on spectral-derived soil attributes, using 2,416 data points on Cd(II), Pb(II), and Cr(VI). The proposed AE-DNN models offer accurate estimations of soil attributes with an average R2 of 0.811 on the independent testing sets. The trained AE-DNN models can reveal patterns typically used by experts to identify bond assignments and promote data-driven knowledge discovery. By comparison with adsorption capacity maps based on actual and estimated soil attributes, we show that the spectral-based soil adsorption capacity evaluation is statistically reliable. Our adsorption capacity maps for the EU and USA identify known soil contamination sites and undocumented areas of high contamination risk. Our framework enables rapid and large-scale prediction of the adsorption capacity of HMs in soil and showcases important guidance for further soil contamination testing, soil management, and industrial planning.
准确、大规模地估算土壤对重金属（HMs）的吸附能力对于解决土壤重金属污染问题至关重要。在此，我们开发了一种新型框架，利用可见光和近红外光谱评估土壤中 HMs 的吸附能力。采用自动编码器（AE）和深度神经网络（DNN）相结合的方法，无需任何光谱预处理即可准确估算出土壤属性。然后，根据光谱得出的土壤属性，使用有关镉（II）、铅（II）和铬（VI）的 2,416 个数据点对土壤 HM 吸附能力进行了评估。所提出的 AE-DNN 模型能准确估计土壤属性，在独立测试集上的平均 R2 为 0.811。训练有素的 AE-DNN 模型可以揭示专家通常用于识别键分配的模式，促进数据驱动的知识发现。通过与基于实际土壤属性和估计土壤属性的吸附容量图进行比较，我们发现基于光谱的土壤吸附容量评估在统计学上是可靠的。我们为欧盟和美国绘制的吸附容量图识别了已知的土壤污染地点和未记录的高污染风险区域。我们的框架能够快速、大规模地预测土壤中 HMs 的吸附容量，并为进一步的土壤污染检测、土壤管理和工业规划提供重要指导。
{"title":"Spectral-Based Machine Learning Enables Rapid and Large-Scale Adsorption Capacity Prediction of Heavy Metals in Soil","authors":"Chongchong Qi, Tao Hu, Mengting Wu, Yong Sik Ok, Han Wang, Liyuan Chai, Zhang Lin","doi":"10.1021/acsestengg.4c00325","DOIUrl":"https://doi.org/10.1021/acsestengg.4c00325","url":null,"abstract":"Accurate and large-scale estimation of the soil adsorption capacity of heavy metals (HMs) is vital to tackle soil HM contamination. Here, a novel framework has been developed to evaluate the adsorption capacity of HMs in soil using visible and near-infrared spectroscopy. Soil attributes were accurately estimated without any spectral preprocessing using a combined autoencoder (AE) and deep neural network (DNN) approach. Soil HM adsorption capability was then evaluated based on spectral-derived soil attributes, using 2,416 data points on Cd(II), Pb(II), and Cr(VI). The proposed AE-DNN models offer accurate estimations of soil attributes with an average <i>R</i><sup>2</sup> of 0.811 on the independent testing sets. The trained AE-DNN models can reveal patterns typically used by experts to identify bond assignments and promote data-driven knowledge discovery. By comparison with adsorption capacity maps based on actual and estimated soil attributes, we show that the spectral-based soil adsorption capacity evaluation is statistically reliable. Our adsorption capacity maps for the EU and USA identify known soil contamination sites and undocumented areas of high contamination risk. Our framework enables rapid and large-scale prediction of the adsorption capacity of HMs in soil and showcases important guidance for further soil contamination testing, soil management, and industrial planning.","PeriodicalId":7008,"journal":{"name":"ACS ES&T engineering","volume":"27 1","pages":""},"PeriodicalIF":7.1,"publicationDate":"2024-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142204236","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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