ACS ES&T engineering最新文献

{"title":"Insight into Redox Sites and Intermolecular Interactions of Soil Dissolved Organic Matter through Diverse-Compost Applications Using VSOMM2 and Schrödinger","authors":"Xinyu Zhao,&nbsp;Beidou Xi*,&nbsp;Yan Wang,&nbsp;Qiuling Dang,&nbsp;Zebin Tian,&nbsp;Danmei Cai and Yun Lu,&nbsp;","doi":"10.1021/acsestengg.4c0047610.1021/acsestengg.4c00476","DOIUrl":"https://doi.org/10.1021/acsestengg.4c00476https://doi.org/10.1021/acsestengg.4c00476","url":null,"abstract":"<p >Substituting chemical fertilizers with compost is anticipated to facilitate the disposal of organic waste and mitigate nonpoint source pollution. However, research investigating the impact of diverse-compost utilization on the chemical reactivity of soil at the molecular-level remains lacking. Herein, the quantification and identification of molecular-scale redox sites and intermolecular interactions of soil dissolved organic matter (DOM) using diverse composts during a crop rotation cycle were investigated using the unified theoretical modeling approach VSOMM2 and Schrödinger. Results showed that compost use considerably altered the molecular weight and composition of soil DOM. In particular, we successfully optimized the validity coefficient of the unit model’s molecular number to construct 38 molecular models of DOM molecules to identify and quantify the distribution of redox sites and intermolecular interactions within soil DOM molecules. Moreover, the distinct roles of different composts in modulating redox molecules within the soil DOM were determined during a crop rotation cycle. The application of cow manure compost considerably increased the quinone, Ar–COOH, and Ar–SH contents in Model(EAC+), while application of food waste compost enhanced the Ar–OH and Ar–NH₂ in Model(EDC+). Finally, rotatable bonds, cation−π interactions, aromatic H-bonds, π-stacking, and salt bridges were identified to facilitate electron transfer within the redox molecules of soil DOM, which can be further enhanced via compost use. The findings of this study provide insights into the environmental biochemical reactions involving microcatalysts, metal reduction fate, pollution fate, and molecular composition of soil, providing a theoretical basis for enhancing soil reactivity using organic fertilizers instead of chemical fertilizers.</p>","PeriodicalId":7008,"journal":{"name":"ACS ES&T engineering","volume":"5 1","pages":"137–148 137–148"},"PeriodicalIF":7.4,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143091819","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}

{"title":"3D g-C3N4/WS2/Agarose Aerogel Photocatalyst for Near-Complete Degradation of Broad-Spectrum Antibiotics in Batch and Continuous Flow Modes","authors":"Mario Vino Lincy Gnanaguru,&nbsp;Debanjali Dey,&nbsp;Makarand M. Ghangrekar,&nbsp;Ramkrishna Sen and Shamik Chowdhury*,&nbsp;","doi":"10.1021/acsestengg.4c0057910.1021/acsestengg.4c00579","DOIUrl":"https://doi.org/10.1021/acsestengg.4c00579https://doi.org/10.1021/acsestengg.4c00579","url":null,"abstract":"<p >Heterojunction-based photocatalysts are receiving tremendous scientific attention for eliminating consumer-derived micropollutants from aqueous environments. However, the inherent difficulty in recovering photocatalysts following treatment, due to their application in powder form, precludes their widespread use. Herein, a self-supporting and lightweight three-dimensional (3D) graphitic carbon nitride (g-C₃N₄)/tungsten disulfide (WS₂)/agarose aerogel (GCWAA) was constructed via a facile and scalable radial freeze-casting approach. The as-synthesized 3D GCWAA proved extremely promising for the photocatalytic removal of three broad-spectrum antibiotic pollutants (ABPs), viz., tetracycline (94%), sulfamethoxazole (97%), and ofloxacin (96%), within 90 min of visible light irradiation in the batch regime. The enhanced photocatalytic performance of 3D GCWAA can be attributed to a Z-scheme electron flow from g-C₃N₄ to WS₂ in the aerogel, as inferred from electronic band structure characterization. To further demonstrate the practical utility of the composite aerogel in water and wastewater treatment systems, the continuous flow photocatalysis of ABPs over 3D GCWAA was systematically studied. Specifically, the influence of several noteworthy operational parameters, such as flow rate, solution pH, and the presence of interfering ions was comprehensively investigated. Interestingly, under optimized conditions, GCWAA achieved a remarkable average removal efficiency of 95% for ABPs in continuous mode, with minimal loss of activity over time. More attractively, GCWAA exhibited decent photocatalytic performance for treating a ternary mixture of ABPs in both freshwaters and wastewaters in the continuous flow reactor. The results of this study showcase the ultimate lab-scale demonstration of the photocatalytic potential of 3D GCWAA for the degradation of emerging contaminants, paving the way for future scale-up.</p>","PeriodicalId":7008,"journal":{"name":"ACS ES&T engineering","volume":"5 2","pages":"515–530 515–530"},"PeriodicalIF":7.4,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143402173","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}

{"title":"Hydrogen Production Promotion from Nonrecyclable Plastic Waste via a Single-Step Catalytic Thermal Cracking/Steam Reforming Scheme","authors":"Mario J. Muñoz-Batista*,&nbsp;Gabriel Blázquez,&nbsp;Rafael R. Solís,&nbsp;Antonio Pérez,&nbsp;M.Ángeles Martín-Lara and Mónica Calero*,&nbsp;","doi":"10.1021/acsestengg.4c0043110.1021/acsestengg.4c00431","DOIUrl":"https://doi.org/10.1021/acsestengg.4c00431https://doi.org/10.1021/acsestengg.4c00431","url":null,"abstract":"<p >A complete analysis of a catalytic pyrolysis scheme, evolved to a combined in situ thermal cracking/steam reforming scheme, to valorize nonrecyclable plastic waste is presented. The study aims to analyze the three fractions obtained, focusing on the production of a hydrogen-rich gaseous fraction with industrial interest. The optimization in terms of hydrogen generation is carried out using various ruthenium-containing catalytic systems prepared by a facile preparation method. Several catalytic systems were tested, all ruthenium-containing materials interacting with g-C₃N₄, ZSM5, high-surface-area carbon, and TiO₂ as active supports. In the combined reaction scheme defined by catalytic cracking/steam reforming reactions at 550 °C of the pyrolysis gases using a RuO₂/TiO₂ composite system in a one-step reaction system, 270.7 mmol of hydrogen (13.5 mmol g^–1 of plastic waste) were obtained, representing an increase of 227.6 mmol in comparison with the traditional thermochemical process. The contribution is completed with a characterization scheme of the obtained product fractions and composite catalysts, including a postreaction analysis, which allowed the identification of the main properties (catalysts) and operating conditions (setup) to optimize the process.</p>","PeriodicalId":7008,"journal":{"name":"ACS ES&T engineering","volume":"5 1","pages":"22–35 22–35"},"PeriodicalIF":7.4,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsestengg.4c00431","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143091621","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"From Literature to Action: Analyzing How Nitrogen and Phosphorus Removal Responds to Different Design Factors in Free Water Surface Constructed Wetlands","authors":"Mohamed S. Gaballah*,&nbsp;Hooshyar Yousefyani and Roderick W. Lammers,&nbsp;","doi":"10.1021/acsestengg.4c0039210.1021/acsestengg.4c00392","DOIUrl":"https://doi.org/10.1021/acsestengg.4c00392https://doi.org/10.1021/acsestengg.4c00392","url":null,"abstract":"<p >Despite the increasing number of studies on nitrogen (N) and phosphorus (P) removal in free water surface (FWS) wetland systems, there is still a gap in understanding the influence of design variables on the system performance. To address this, we conducted a global meta-analysis of 73 studies employing advanced statistical techniques, kinetic models, and machine learning along with variable importance analysis. The results indicated that random forest (<i>R</i>² = 0.55–0.77) and artificial neural network (<i>R</i>² = 0.5–0.85) were the best fitting models for TN and TP removal in pilot-scale and large-scale systems. Moreover, permutation importance results using different wetland design variables indicated that the inflow concentration, plant coverage, hydraulic loading rate, and system area are considered the most important variables for N and P removal under large-scale conditions, while the hydraulic retention time, inflow concentration, and water depth are deemed the most important variables under pilot-scale conditions. Furthermore, the removal of N and P was higher in pilot-scale (54.6% and 56.7%) systems compared to that in large-scale (29.0% and 41.9%) systems. Also, the interactions between design variables and the removal process of N and P were investigated to better understand the specific roles of these variables in improving the removal performance.</p>","PeriodicalId":7008,"journal":{"name":"ACS ES&T engineering","volume":"4 12","pages":"2974–2986 2974–2986"},"PeriodicalIF":7.4,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsestengg.4c00392","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142851215","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nickel Enhances InPd-Catalyzed Nitrate Reduction Activity and N2 Selectivity","authors":"Kiheon Hong,&nbsp;Daniel J. Rivera,&nbsp;Juan Donoso,&nbsp;Bongki Shin,&nbsp;Hunter P. Jacobs,&nbsp;Byeong Jun Cha,&nbsp;Kimberly N. Heck,&nbsp;Welman C. Elias,&nbsp;Paul Westerhoff,&nbsp;Yimo Han,&nbsp;Christopher Muhich and Michael S. Wong*,&nbsp;","doi":"10.1021/acsestengg.4c0055210.1021/acsestengg.4c00552","DOIUrl":"https://doi.org/10.1021/acsestengg.4c00552https://doi.org/10.1021/acsestengg.4c00552","url":null,"abstract":"<p >Palladium–indium (PdIn) is a well-established bimetallic composition for reductively degrading nitrate anions, one of the most ubiquitous contaminants in the groundwater. However, the scarcity and the variable price of these rare-earth and platinum group critical metals may hinder their use for water treatment. Nickel (Ni), a nonprecious metal in the same element group as Pd, could partially replace and lower Pd usage if the resulting trimetallic composition is sufficiently catalytically active. Herein, we report the synthesis and nitrate reduction catalysis of activated carbon-supported “In-on-Pd-on-Ni” catalysts (InPdNi/AC). While bimetallic InPd/AC (0.05 wt % In, 1.3 wt % Pd) was expectedly active, trimetallic InPdNi/AC containing the same In amount, much less Pd (0.1 wt %), and 1 wt % Ni was &gt;17 more active (<i>k</i>_cat ≈ 20 vs 349 L min^–1 g_{surface metal}^–1). X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations showed that Pd gained electron density from Ni, correlating to the increased nitrate reduction activity. Ammonium byproduct selectivity for InPdNi/AC (18% at 50% nitrate conversion) was lower compared to that of InPd/AC (48%), suggestive of the higher surface coverage of NO or its greater reactivity with NO₂^–, which led to more N₂. Accounting for the catalyst precursor, manufacturing costs, and spent metal recovery, we calculated that Ni incorporation lowered the net catalyst cost significantly (from $1028/kg to $170/kg). The trimetallic composition lowered, by ∼26 times, the catalyst cost of a stirred tank reactor sized to the same treatment capacity as that for the bimetallic case. The results demonstrate that the partial replacement of the precious metal with an earth-abundant one leads to a higher efficiency and lower cost denitrification catalyst, via a material strategy that should be beneficial for other clean-water catalytic systems.</p>","PeriodicalId":7008,"journal":{"name":"ACS ES&T engineering","volume":"5 2","pages":"434–446 434–446"},"PeriodicalIF":7.4,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143402172","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}

{"title":"Electron Donor-Driven Microalgae Upgrading into High-Value Fatty Acids via a Microbial Platform","authors":"Chen Wang,&nbsp;Wei Wei*,&nbsp;Lan Wu,&nbsp;Xiaoqing Liu,&nbsp;Haoran Duan,&nbsp;Zhijie Chen,&nbsp;Ya-Nan Hou,&nbsp;Xueming Chen and Bing-Jie Ni*,&nbsp;","doi":"10.1021/acsestengg.4c0041410.1021/acsestengg.4c00414","DOIUrl":"https://doi.org/10.1021/acsestengg.4c00414https://doi.org/10.1021/acsestengg.4c00414","url":null,"abstract":"<p >The efficient treatment and energy recovery from salvaged microalgae have been imperative considering both environmental and economic concerns. Herein, this study proposed a biotechnological platform for converting microalgae into medium-chain fatty acids (MCFAs) through anaerobic fermentation as well as exploring the roles of different electron donors (EDs). After exploring various ED combinations, the results suggested that a single ED, especially sole ethanol stimulation, exhibited more pronounced stimulation effects on MCFA production compared to those of the hybrid ED stimulations. Furthermore, ethanol and lactic acid served as the basis for the formation of longer-chain alcohols and odd-chain fatty acids in the liquid fermentation products, respectively. The dynamics and thermodynamics analyses confirmed the distinctions in the accumulation trends and saturated compositions of main products under different ED compositions. Moreover, mechanistic investigations revealed that differences in chain elongation efficiency of ethanol and lactic acid and in the genome-based metabolic potential for the microbial systems contributed to the intricate feedback regulations of biochemical reactions in different microalgae fermentation scenarios. Overall, this study provided valuable insights for sustainable energy conversion of microalgae by orienting toward the recovery of high-value biochemicals, serving as a theoretical basis for the selection and optimization of ED before industrial application.</p>","PeriodicalId":7008,"journal":{"name":"ACS ES&T engineering","volume":"4 12","pages":"3080–3091 3080–3091"},"PeriodicalIF":7.4,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142851225","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}

{"title":"Mitigation of Pharmaceutical Wastewater Toxicity in Anaerobic Reactors Using Metal-Modified Biochar","authors":"Ahmed Tawfik*,&nbsp;Nawaf S. Alhajeri,&nbsp;Mohamed Elsamadony* and Fangang Meng,&nbsp;","doi":"10.1021/acsestengg.4c0039310.1021/acsestengg.4c00393","DOIUrl":"https://doi.org/10.1021/acsestengg.4c00393https://doi.org/10.1021/acsestengg.4c00393","url":null,"abstract":"<p >Anaerobic sequencing batch reactors (ASBRs) treating wastewater rich in ciprofloxacin (CIP) were supplemented with an Fe/Zn@biochar catalyst to improve their performance. ASBR4, with 100 mg Fe/Zn@biochar/g_VS, showed substantial increased efficiencies in removing COD and CIP, reaching 86.9 ± 5.8 and 80.9 ± 8.6%, respectively, compared to no biochar addition (25.2% and 51.1% higher, respectively). Likewise, biogas yield augmented from 0.17 ± 0.06 to 0.34 ± 0.02 L/g COD_removed owing to the boosted abundance of acetolactic methanogens, i.e., <i>Methanosaeta</i> and <i>Methanosarcina</i>, which increased from 0.4 and 1.6% in the control ASBR1 to 1.6 and 2.2% in ASBR4, respectively. Microbial enzymatic activities, including dehydrogenase and extracellular polymeric substances (EPSs), highly increased by 38% and &gt;100%, respectively, aiding in biochar adsorption and microbial biodegradation synergy. Fe/Zn@biochar contributed to both CIP adsorption and biodegradation with percentages of 59.5 ± 4.9 and 34.7 ± 2.6%, respectively. The synergistic effect between the biotic and abiotic impacts of Fe/Zn@biochar reached 94.2 ± 7.2%, suggesting that the addition of Fe/Zn@biochar is a promising approach to enhance the CIP-remediation process.</p>","PeriodicalId":7008,"journal":{"name":"ACS ES&T engineering","volume":"4 12","pages":"2987–3000 2987–3000"},"PeriodicalIF":7.4,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142851224","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}

{"title":"Molecular-Level Explanation of AOM Removal by a Composite Coagulant Based on the Subdivision of Organic Components","authors":"Siyu Zhang,&nbsp;Kangying Guo,&nbsp;Beibei Liu,&nbsp;Yue Gao,&nbsp;Qinyan Yue and Baoyu Gao*,&nbsp;","doi":"10.1021/acsestengg.4c0055910.1021/acsestengg.4c00559","DOIUrl":"https://doi.org/10.1021/acsestengg.4c00559https://doi.org/10.1021/acsestengg.4c00559","url":null,"abstract":"<p >Algal organic matter (AOM), comprising intracellular organic matter (IOM) and extracellular organic matter (EOM), poses a significant challenge to drinking water safety. Coagulation serves as an effective method for removing algae, and investigating the binding sites of coagulant hydrolyzates is crucial for comprehending the coagulation mechanism. In this study, a novel polyferric titanium sulfate (PFTS) composite coagulant was prepared and used to remove AOM. Characterization techniques, including Fourier infrared (FTIR), X-ray photoelectron spectroscopy (XPS), hydrolysis polymerization curves, and chemical species analysis were utilized to identify the hydrolyzates of PFTS. The results revealed the formation of Fe–Ti copolymers through the interaction between Fe hydroxyl and Ti hydroxyl, facilitated by a Fe–O–Ti bond. Under optimal coagulation conditions (50 mg/L dosage at neutral pH), PFTS demonstrated superior performance in treating EOM and IOM compared to PFS and PTS, achieving significant DOC removal efficiencies of 46.69% and 56.8%, respectively. Furthermore, the removal characteristics of organics were investigated at the molecular level using Fourier transformation cyclotron resonance mass spectrometry (FT-ICR MS). It was found that organic compounds with unsaturated (H/C &lt; 1.0) and oxidized (O/C &gt; 0.5) substances containing carboxyl groups in AOM could be preferentially removed by PFTS for the carboxyl group demonstrate a higher affinity to Fe and Ti hydroxyl formed in PFTS coagulation. XPS and water contact angle analysis were conducted to gain deeper insights into the interaction between the hydrolyzates of PFTS and AOM. The findings demonstrated that Fe–Ti hydrolyzates could bind with EOM and IOM by forming coordination bonds and H–O···O and H–O···N hydrogen bonds with its −COOH, −NH₂, and −OH groups through bonding reactions. This study highlights the potential of composite coagulants as alternatives to conventional coagulants for the purification of algae-laden water.</p>","PeriodicalId":7008,"journal":{"name":"ACS ES&T engineering","volume":"5 2","pages":"456–467 456–467"},"PeriodicalIF":7.4,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143402171","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}

{"title":"Enhanced Medium-Chain Fatty Acids Production by Electro-fermentation: Insights into the Effect of Biocathode and Ethanol Supply","authors":"Xiaoyan Sun,&nbsp;Yanan Yin*,&nbsp;Hui Chen,&nbsp;Lei Zhao,&nbsp;Cheng Wang and Jianlong Wang,&nbsp;","doi":"10.1021/acsestengg.4c0048810.1021/acsestengg.4c00488","DOIUrl":"https://doi.org/10.1021/acsestengg.4c00488https://doi.org/10.1021/acsestengg.4c00488","url":null,"abstract":"<p >This study explored the enhanced medium-chain fatty acids (MCFA) production by introducing a biocathode as a coelectron donor (ED) in the presence of different ethanol/acetate ratios (<i>R</i>_E/A). Results showed that the introduction of a biocathode effectively promoted MCFA production by 165%–749%. The highest promotion rate was achieved at <i>R</i>_E/A = 0:3, and the highest MCFA concentration of 305.1 mmol C/L was obtained at <i>R</i>_E/A = 2:1. Besides, the introduction of a biocathode also triggered the formation of longer-chain MCFA (i.e., caprylate), and caprylate production was increased with the increase of <i>R</i>_E/A. Electrochemical analyses exhibited a positive correlation between the electrochemical activity and <i>R</i>_E/A. Microbiological analyses showed that the introduction of a biocathode promoted MCFA production by enriching chain elongation functional microorganisms (<i>unclassified_f_Neisseriaceae</i> sp. and <i>Clostridium_sensu_stricto_12</i> sp.) and electrochemically active bacteria (<i>Alcaligenes</i> sp.). Enzyme analyses indicated that promoted MCFA production was achieved by strengthening the acetyl Co-A formation and fatty acid biosynthesis pathway.</p>","PeriodicalId":7008,"journal":{"name":"ACS ES&T engineering","volume":"5 1","pages":"179–190 179–190"},"PeriodicalIF":7.4,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143091721","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}

{"title":"Single-Atom Copper-Bearing Cerium Oxide Electrocatalysts Embedded in an Integrated System Enable Sustainable Nitrogen Recycling from Natural Water Bodies","authors":"Guangming Jiang*,&nbsp;Zixun Liu,&nbsp;Shuxian He,&nbsp;Yinan Liu,&nbsp;Xiangyi Tang,&nbsp;Xiaoshu Lv,&nbsp;Fan Dong and Hong Liu*,&nbsp;","doi":"10.1021/acsestengg.4c0029910.1021/acsestengg.4c00299","DOIUrl":"https://doi.org/10.1021/acsestengg.4c00299https://doi.org/10.1021/acsestengg.4c00299","url":null,"abstract":"<p >Electrocatalytic reduction of nitrate (NO₃^–) to ammonia (NH₃) (NO₃RR) coupled with NH₃ separation represents a sustainable approach to mitigate nitrate pollution and recycle nitrogen from contaminated water. Nevertheless, this process is deemed impractical for contaminated natural water bodies owing to the limited presence of NO₃^––N (&lt;50 mg L^–1) and electrolytes and the relative abundance of scaling ions (Mg²⁺ and Ca²⁺). Furthermore, copper (Cu), as the primary NO₃RR catalyst, generally suffers from NO₂^– accumulation and a prevalence of side hydrogen evolution. Herein, we develop an integrated system comprising sections of NO₃^– enrichment and NO₃RR and NH₃ collection, alongside a single-atom Cu-bearing CeO₂ catalyst (Cu₁/CeO₂) for NO₃RR. With this system, diluted NO₃^– is extracted from contaminated water using anion-exchange resins and then released into a concentrated NaCl aqueous solution, providing a solution with ample NO₃^––N (∼822 mg L^–1) and electrolytes (∼1.7 M NaCl) while being free of scaling ions. Within this solution, the Cu₁/CeO₂ demonstrates an exceptional high and steady NH₃–N production rate of 7.8 g_NH₃–N g_Cu^–1 h^–1, an NH₃–N selectivity of 90.1%, and a Faradaic efficiency of 91.3%, outperforming the Cu nanoparticles (1.8 g_NH₃–N g_Cu^–1 h^–1, 46.3%, and 53.0%). In situ experiments and theoretical computations reveal a dual-site NO₃RR mechanism involving the electron-deficient Cu₁ site and adjacent oxygen vacancies, which collaborate to promote NO₃^– adsorption and lower conversion barrier while inhibiting hydrogen evolution. Finally, we implemented the integrated system along the Yangtze River, achieving nitrate elimination and nitrogen recycling with a competitive energy consumption of 1.36–1.54 kW h mol_N^–1.</p>","PeriodicalId":7008,"journal":{"name":"ACS ES&T engineering","volume":"4 12","pages":"2912–2922 2912–2922"},"PeriodicalIF":7.4,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142851178","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}