A series of CuFe and Ag-modified CuFe composite catalysts were prepared for low-temperature selective catalytic oxidation of ammonia (NH3-SCO). Significant synergistic effects existed between Cu and Fe oxides in the CuFe(7:12) catalyst for catalyzing NH3 oxidation. Loading 6 wt.% Ag over CuFe(7:12) further enhanced NH3 conversion and N2 selectivity. At 200 °C, NH3 conversion and N2 selectivity reached 97.1 % and 79.3 %, respectively, over 6Ag/CuFe(7:12). Besides the exceptional catalytic effects of Ag species, the increased surface area, formation of CuFe2O4, improved reducibility of Cu and Fe oxides, and increased acid sites due to the composite of Cu and Fe and modification with Ag contributed to the superior performance of the 6Ag/CuFe(7:12) catalyst in NH3-SCO. In-situ DRIFTS results showed that NH3 oxidation might follow the internal selective catalytic reduction mechanism: NH3 was dehydrogenated and oxidized to NOx and nitrate species, and the formed NOx and nitrate species were reduced by the remaining NH3, −NH2 and −NH species to N2 and H2O. Loading Ag over CuFe(7:12) suppressed the formation of NO and NO2 but promoted that of N2O during NH3 oxidation, which could be attributed to the enhanced formation and decomposition of NH4NO3 in the presence of Ag.
制备了一系列 CuFe 和 Ag 改性 CuFe 复合催化剂，用于氨（NH3-SCO）的低温选择性催化氧化。CuFe(7:12) 催化剂中的铜和铁氧化物在催化 NH3 氧化方面具有显著的协同效应。在 CuFe(7:12) 中添加 6 wt.% 的 Ag 可进一步提高 NH3 转化率和 N2 选择性。200 °C 时，6Ag/CuFe(7:12) 的 NH3 转化率和 N2 选择性分别达到 97.1 % 和 79.3 %。6Ag/CuFe(7:12) 催化剂之所以能在 NH3-SCO 中表现出卓越的性能，除了 Ag 物种的特殊催化作用外，其表面积的增加、CuFe2O4 的形成、Cu 和 Fe 氧化物还原性的改善以及 Cu 和 Fe 的复合和 Ag 的修饰所带来的酸性位点的增加也功不可没。原位 DRIFTS 结果表明，NH3 氧化可能遵循内选择性催化还原机制：NH3 被脱氢并氧化成 NOx 和硝酸盐，形成的 NOx 和硝酸盐被剩余的 NH3、-NH2 和 -NH 还原成 N2 和 H2O。在 CuFe（7:12）上添加 Ag 可抑制 NH3 氧化过程中 NO 和 NO2 的形成，但会促进 N2O 的形成，这可能是由于在 Ag 的存在下 NH4NO3 的形成和分解得到了增强。
{"title":"Ag-modified CuO-Fe2O3 composite catalysts for low-temperature NH3-SCO","authors":"Ruixue Guo, Xing Fan, Jianyu Cai, Shuangye Li, Yanli Zhang, Jiasheng Liu, Jian Li","doi":"10.1016/j.surfin.2024.105371","DOIUrl":"10.1016/j.surfin.2024.105371","url":null,"abstract":"<div><div>A series of CuFe and Ag-modified CuFe composite catalysts were prepared for low-temperature selective catalytic oxidation of ammonia (NH<sub>3</sub>-SCO). Significant synergistic effects existed between Cu and Fe oxides in the CuFe(7:12) catalyst for catalyzing NH<sub>3</sub> oxidation. Loading 6 wt.% Ag over CuFe(7:12) further enhanced NH<sub>3</sub> conversion and N<sub>2</sub> selectivity. At 200 °C, NH<sub>3</sub> conversion and N<sub>2</sub> selectivity reached 97.1 % and 79.3 %, respectively, over 6Ag/CuFe(7:12). Besides the exceptional catalytic effects of Ag species, the increased surface area, formation of CuFe<sub>2</sub>O<sub>4</sub>, improved reducibility of Cu and Fe oxides, and increased acid sites due to the composite of Cu and Fe and modification with Ag contributed to the superior performance of the 6Ag/CuFe(7:12) catalyst in NH<sub>3</sub>-SCO. <em>In-situ</em> DRIFTS results showed that NH<sub>3</sub> oxidation might follow the internal selective catalytic reduction mechanism: NH<sub>3</sub> was dehydrogenated and oxidized to NO<em><sub>x</sub></em> and nitrate species, and the formed NO<em><sub>x</sub></em> and nitrate species were reduced by the remaining NH<sub>3</sub>, −NH<sub>2</sub> and −NH species to N<sub>2</sub> and H<sub>2</sub>O. Loading Ag over CuFe(7:12) suppressed the formation of NO and NO<sub>2</sub> but promoted that of N<sub>2</sub>O during NH<sub>3</sub> oxidation, which could be attributed to the enhanced formation and decomposition of NH<sub>4</sub>NO<sub>3</sub> in the presence of Ag.</div></div>","PeriodicalId":22081,"journal":{"name":"Surfaces and Interfaces","volume":"55 ","pages":"Article 105371"},"PeriodicalIF":5.7,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142571620","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-29DOI: 10.1016/j.surfin.2024.105368
Xiaoxia Li , Rongrong Hu , Xiong Zhou , Zhengyuan Liu , Shuaiqi Zhao , Aimal Khan , Wei Li , Zhongduo Xiong , Aihua Xu
Permanganate (PM) activation to remove contaminants in aqueous solution has gained increasing interest, and effective approaches to enhance its oxidation ability are becoming one of the hot spots. Transition metal oxides (TMOs) stand out as the most potential catalysts, but have received little attention in this area until now. Their mechanism towards PM activation also remains controversial. In this study, a series of TMOs with diverse surface properties were synthesized, and their effectiveness was compared. It was observed that α-MnO2, NiO and Co3O4 exhibited significantly higher rates of degrading sulfadiazine, levofloxacin and phenol through PM activation than CeO2, α-Fe2O3 and CuO. A performance evolution depended on the surface Lewis acid (LA) strength was established, while a less consistent correlation was observed between the degradation rate and other surface properties. Based on electrochemical analysis and density functional theory calculations, the spontaneous adsorption of MnO4- anions on LA sites in TMOs with an increase in oxidation potential of PM was further confirmed. This research would deepen the understanding of PM activation mechanism, and offer new guidance in the design of more efficient catalysts.
{"title":"Influence of surface properties of transition metal oxides for permanganate activation: Key role of Lewis acid sites","authors":"Xiaoxia Li , Rongrong Hu , Xiong Zhou , Zhengyuan Liu , Shuaiqi Zhao , Aimal Khan , Wei Li , Zhongduo Xiong , Aihua Xu","doi":"10.1016/j.surfin.2024.105368","DOIUrl":"10.1016/j.surfin.2024.105368","url":null,"abstract":"<div><div>Permanganate (PM) activation to remove contaminants in aqueous solution has gained increasing interest, and effective approaches to enhance its oxidation ability are becoming one of the hot spots. Transition metal oxides (TMOs) stand out as the most potential catalysts, but have received little attention in this area until now. Their mechanism towards PM activation also remains controversial. In this study, a series of TMOs with diverse surface properties were synthesized, and their effectiveness was compared. It was observed that α-MnO<sub>2</sub>, NiO and Co<sub>3</sub>O<sub>4</sub> exhibited significantly higher rates of degrading sulfadiazine, levofloxacin and phenol through PM activation than CeO<sub>2</sub>, α-Fe<sub>2</sub>O<sub>3</sub> and CuO. A performance evolution depended on the surface Lewis acid (LA) strength was established, while a less consistent correlation was observed between the degradation rate and other surface properties. Based on electrochemical analysis and density functional theory calculations, the spontaneous adsorption of MnO<sub>4</sub><sup>-</sup> anions on LA sites in TMOs with an increase in oxidation potential of PM was further confirmed. This research would deepen the understanding of PM activation mechanism, and offer new guidance in the design of more efficient catalysts.</div></div>","PeriodicalId":22081,"journal":{"name":"Surfaces and Interfaces","volume":"55 ","pages":"Article 105368"},"PeriodicalIF":5.7,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142571365","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-29DOI: 10.1016/j.surfin.2024.105365
Xuewen An, Yujun Hou, Weijia An, Jinshan Hu, Huan Wang, Wenquan Cui
Fe-Cu bimetal materials exhibit high catalytic degradation activity with more active sites, faster charge transfer efficiency and synergistic effects on redox pairs. However, it faces the problems of easy compounding and instability. Therefore, we designed and synthesized Fe-Cu/TiO2 composite catalysts and constructed a synergistic photocatalytic-persulfate degradation system. The phenol (50 ppm) degradation efficiency of 70 % Fe-Cu/TiO2 was 97.3 % after 30 min of reaction, which was 1.49 and 16.51 times greater than those of Fe-Cu and TiO2, respectively. This was attributed to the fact that mixing TiO2 and Fe-Cu not only effectively promoted Fe-Cu dispersion but also improved the number of active sites and catalytic degradation activity. Moreover, the photogenerated electrons generated by TiO2 could promote the valence transition between Fe-Cu, slowly releasing Fe2+ and Cu0 to realize the continuous activation of PDS and enhance the degradation activity. Quenching experiments and EPR results showed that the catalytic degradation process was dominated by the nonradical 1O2, with SO4·-, ·OH and ·O2- radicals interacting synergistically. Based on the characterization and experimental results, a synergistic degradation mechanism of Fe-Cu/TiO2 was proposed, which provides a new approach for pollutant degradation.
{"title":"Mechanism of TiO2 stabilization and promotion of the synergistic zero-valent Fe‒Cu photocatalysis-persulfate degradation of phenol","authors":"Xuewen An, Yujun Hou, Weijia An, Jinshan Hu, Huan Wang, Wenquan Cui","doi":"10.1016/j.surfin.2024.105365","DOIUrl":"10.1016/j.surfin.2024.105365","url":null,"abstract":"<div><div>Fe-Cu bimetal materials exhibit high catalytic degradation activity with more active sites, faster charge transfer efficiency and synergistic effects on redox pairs. However, it faces the problems of easy compounding and instability. Therefore, we designed and synthesized Fe-Cu/TiO<sub>2</sub> composite catalysts and constructed a synergistic photocatalytic-persulfate degradation system. The phenol (50 ppm) degradation efficiency of 70 % Fe-Cu/TiO<sub>2</sub> was 97.3 % after 30 min of reaction, which was 1.49 and 16.51 times greater than those of Fe-Cu and TiO<sub>2</sub>, respectively. This was attributed to the fact that mixing TiO<sub>2</sub> and Fe-Cu not only effectively promoted Fe-Cu dispersion but also improved the number of active sites and catalytic degradation activity. Moreover, the photogenerated electrons generated by TiO<sub>2</sub> could promote the valence transition between Fe-Cu, slowly releasing Fe<sup>2+</sup> and Cu<sup>0</sup> to realize the continuous activation of PDS and enhance the degradation activity. Quenching experiments and EPR results showed that the catalytic degradation process was dominated by the nonradical <sup>1</sup>O<sub>2</sub>, with SO<sub>4</sub>·<sup>-</sup>, ·OH and ·O<sub>2</sub><sup>-</sup> radicals interacting synergistically. Based on the characterization and experimental results, a synergistic degradation mechanism of Fe-Cu/TiO<sub>2</sub> was proposed, which provides a new approach for pollutant degradation.</div></div>","PeriodicalId":22081,"journal":{"name":"Surfaces and Interfaces","volume":"55 ","pages":"Article 105365"},"PeriodicalIF":5.7,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142571613","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-29DOI: 10.1016/j.surfin.2024.105309
Rana Saad , Khaled Abdelkarem , Mohamed Shaban , Adel M. El Sayed , Inas A. Ahmed , Mohamed T. Tammam , Hany Hamdy
The urgency to address climate change has highlighted the need for gas sensors capable of monitoring air quality at room temperature (RT) and accurately measuring the concentrations of carbon oxides (CO2 and CO) in the environment. This study details the development of a highly sensitive CO2 gas sensor using spin-coated Sn-doped Co3O4 thin films, operating at a room temperature of 30⁰C and a relative humidity (RH%) of 43 %. Extensive characterization employing XRD, SEM, EDX, FTIR, and UV–Vis optical techniques verified the impact of Sn doping on the surface morphology, phase purity, and a notable reduction in the dual-band gap of the thin films. Gas sensing measurements were conducted at RT using varying CO2 gas concentrations. A sensor response of 796.81 % was obtained for the optimally sensitive film, 10 % Sn-doped Co3O4, at a CO2 concentration of 9990 ppm. Additionally, a range of RH % levels was examined at a constant CO2 gas concentration of 9990 ppm, revealing an optimal humidity level of 43 % at RT. Further analysis revealed that the 10 % Sn-Co3O4 sensor displayed enhanced sensitivity to CO2, surpassing its response to N2, H2, and NH3 gases. The determined limits of detection and quantification underscore the sensor's precision and reliability in quantifying CO2 gas concentrations. Our findings demonstrate the excellent potential of Sn-doped Co₃O₄ thin films as highly sensitive CO₂ gas sensors. These films provide a promising solution for detecting elevated CO₂ levels at room temperature, aiding climate change mitigation efforts.
{"title":"Highly sensitive and room-temperature operable carbon dioxide gas sensor based on spin-coated Sn-doped Co3O4 thin films with advanced recovery properties","authors":"Rana Saad , Khaled Abdelkarem , Mohamed Shaban , Adel M. El Sayed , Inas A. Ahmed , Mohamed T. Tammam , Hany Hamdy","doi":"10.1016/j.surfin.2024.105309","DOIUrl":"10.1016/j.surfin.2024.105309","url":null,"abstract":"<div><div>The urgency to address climate change has highlighted the need for gas sensors capable of monitoring air quality at room temperature (RT) and accurately measuring the concentrations of carbon oxides (CO<sub>2</sub> and CO) in the environment. This study details the development of a highly sensitive CO<sub>2</sub> gas sensor using spin-coated Sn-doped Co<sub>3</sub>O<sub>4</sub> thin films, operating at a room temperature of 30⁰C and a relative humidity (RH%) of 43 %. Extensive characterization employing XRD, SEM, EDX, FTIR, and UV–Vis optical techniques verified the impact of Sn doping on the surface morphology, phase purity, and a notable reduction in the dual-band gap of the thin films. Gas sensing measurements were conducted at RT using varying CO<sub>2</sub> gas concentrations. A sensor response of 796.81 % was obtained for the optimally sensitive film, 10 % Sn-doped Co<sub>3</sub>O<sub>4</sub>, at a CO<sub>2</sub> concentration of 9990 ppm. Additionally, a range of RH % levels was examined at a constant CO<sub>2</sub> gas concentration of 9990 ppm, revealing an optimal humidity level of 43 % at RT. Further analysis revealed that the 10 % Sn-Co<sub>3</sub>O<sub>4</sub> sensor displayed enhanced sensitivity to CO<sub>2</sub>, surpassing its response to N<sub>2</sub>, H<sub>2</sub>, and NH<sub>3</sub> gases. The determined limits of detection and quantification underscore the sensor's precision and reliability in quantifying CO<sub>2</sub> gas concentrations. Our findings demonstrate the excellent potential of Sn-doped Co₃O₄ thin films as highly sensitive CO₂ gas sensors. These films provide a promising solution for detecting elevated CO₂ levels at room temperature, aiding climate change mitigation efforts.</div></div>","PeriodicalId":22081,"journal":{"name":"Surfaces and Interfaces","volume":"55 ","pages":"Article 105309"},"PeriodicalIF":5.7,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142660720","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-28DOI: 10.1016/j.surfin.2024.105357
Neeraj Dhariwal, Vinod Kumar
Pristine and Cr-doped α-Fe2O3 nanoparticles were synthesized using a low-cost and simple one-step hydrothermal method without any precipitating agent. Cr-doped α-Fe2O3 was found to be a promising candidate for recyclable photocatalytic application for Tetracycline (TC) and Congo-red (CR) degradation under normal sunlight irradiation along with excellent antibacterial properties. Addition of Cr shows a significantly improved degradation efficiency from 20% to 91% in just 25 min for CR, while the degradation rate reached to 81% for TC, which was also monitored in real-time using internet of things (IoT). Also, a high degree of mineralization was achieved (∼87.9%), which was confirmed using total organic carbon (TOC) content. In parallel, the biochemical oxygen demand/chemical oxygen demand (BOD5/COD) ratio confirmed the fast degradation efficiency using a small amount of catalytic dosage (∼ 0.40 g/L). Also, degradation of multiple dyes provides a promising avenue for addressing complex waste water treatment challenges. Moreover, Cr-doped α-Fe2O3 displays excellent antibacterial activity towards E.coli and E.Faecium. Major factors involved in sunlight driven photocatalytic activity for example absorbance range, porosity, separation between e--h+, and charge transfer property were surprisingly improved by Cr doping and henceforth increased photocatalytic activity and antibacterial properties. This work highlights the potential utilization of Cr-doped α-Fe2O3 for the purification and disinfection of industrial waste water.
{"title":"Cr3+doped α-Fe2O3 nanoparticles for photodegradation of organic pollutants with their disinfection efficacy","authors":"Neeraj Dhariwal, Vinod Kumar","doi":"10.1016/j.surfin.2024.105357","DOIUrl":"10.1016/j.surfin.2024.105357","url":null,"abstract":"<div><div>Pristine and Cr-doped α-Fe<sub>2</sub>O<sub>3</sub> nanoparticles were synthesized using a low-cost and simple one-step hydrothermal method without any precipitating agent. Cr-doped α-Fe<sub>2</sub>O<sub>3</sub> was found to be a promising candidate for recyclable photocatalytic application for Tetracycline (TC) and Congo-red (CR) degradation under normal sunlight irradiation along with excellent antibacterial properties. Addition of Cr shows a significantly improved degradation efficiency from 20% to 91% in just 25 min for CR, while the degradation rate reached to 81% for TC, which was also monitored in real-time using internet of things (IoT). Also, a high degree of mineralization was achieved (∼87.9%), which was confirmed using total organic carbon (TOC) content. In parallel, the biochemical oxygen demand/chemical oxygen demand (BOD<sub>5</sub>/COD) ratio confirmed the fast degradation efficiency using a small amount of catalytic dosage (∼ 0.40 g/L). Also, degradation of multiple dyes provides a promising avenue for addressing complex waste water treatment challenges. Moreover, Cr-doped α-Fe<sub>2</sub>O<sub>3</sub> displays excellent antibacterial activity towards E.coli and E.Faecium. Major factors involved in sunlight driven photocatalytic activity for example absorbance range, porosity, separation between e<sup>-</sup>-<em>h</em><sup>+</sup>, and charge transfer property were surprisingly improved by Cr doping and henceforth increased photocatalytic activity and antibacterial properties. This work highlights the potential utilization of Cr-doped α-Fe<sub>2</sub>O<sub>3</sub> for the purification and disinfection of industrial waste water.</div></div>","PeriodicalId":22081,"journal":{"name":"Surfaces and Interfaces","volume":"55 ","pages":"Article 105357"},"PeriodicalIF":5.7,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142571678","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-28DOI: 10.1016/j.surfin.2024.105327
B. Salameh , A.M. Alsmadi
Antimony-doped tin oxide (Sb:SnO2) thin films with varying Sb concentrations were deposited using the spray pyrolysis technique. A comprehensive analysis of the films' elemental, structural, and optoelectronic properties is presented. All films possess a polycrystalline single-phase nature and have a tetragonal rutile structure. As Sb concentration increases, the unit cell shrinks continuously, suggesting proper substitution of Sn4+ by Sb5+. This substitution causes a continuous increase in the concentration of charge carriers and a reduction in electron mobility. X-ray photoelectron spectroscopy investigations revealed the presence of asymmetric Sn 3d core-level peaks distinguished by peak splitting, which increases with increasing carrier concentration. Utilizing the plasmon absorption model, an effective mass value of (0.51 ± 0.07)me for the conduction electron at the fermi level is obtained. With increasing Sb concentration, the optical energy gap increases gradually from 3.84 eV for undoped SnO2 to 4.35 eV for 5.0 at. % Sb. After considering the Urbach tailing phenomenon as well as the Moss–Burstein effect, this increase was attributed to the increase in Moss–Burstein energy due to increased charge carrier concentration. Our study revealed that the film doped with 2.0 at. % Sb has the best optoelectronic properties, with a figure of merit of 4.18 (Ω/cm2)−1.
利用喷雾热解技术沉积了不同锑浓度的掺锑氧化锡（Sb:SnO2）薄膜。本文对薄膜的元素、结构和光电特性进行了全面分析。所有薄膜都具有多晶单相性质，并具有四方金红石结构。随着锑浓度的增加，单位晶胞不断缩小，这表明 Sb5+ 适当地取代了 Sn4+。这种置换导致电荷载流子浓度持续上升，电子迁移率降低。X 射线光电子能谱研究表明，存在非对称的 Sn 3d 核心级峰，其区别在于峰分裂，且随着载流子浓度的增加而增加。利用等离子体吸收模型，得到费米级传导电子的有效质量值为 (0.51 ± 0.07)me。随着掺锑浓度的增加，光学能隙从未掺锑二氧化锡的 3.84 eV 逐渐增加到掺锑 5.0 at.在考虑了乌尔巴赫拖尾现象和莫斯-伯斯坦效应后，这一增加归因于电荷载流子浓度增加导致的莫斯-伯斯坦能的增加。我们的研究表明，掺杂 2.0%锑的薄膜具有最佳的光电特性，其优越性为 4.18 (Ω/cm2)-1。
{"title":"Enhanced optoelectronic properties of spray deposited antimony-doped tin oxide thin films","authors":"B. Salameh , A.M. Alsmadi","doi":"10.1016/j.surfin.2024.105327","DOIUrl":"10.1016/j.surfin.2024.105327","url":null,"abstract":"<div><div>Antimony-doped tin oxide (Sb:SnO<sub>2</sub>) thin films with varying Sb concentrations were deposited using the spray pyrolysis technique. A comprehensive analysis of the films' elemental, structural, and optoelectronic properties is presented. All films possess a polycrystalline single-phase nature and have a tetragonal rutile structure. As Sb concentration increases, the unit cell shrinks continuously, suggesting proper substitution of Sn<sup>4+</sup> by Sb<sup>5+</sup>. This substitution causes a continuous increase in the concentration of charge carriers and a reduction in electron mobility. X-ray photoelectron spectroscopy investigations revealed the presence of asymmetric Sn 3d core-level peaks distinguished by peak splitting, which increases with increasing carrier concentration. Utilizing the plasmon absorption model, an effective mass value of (0.51 ± 0.07)<em>m<sub>e</sub></em> for the conduction electron at the fermi level is obtained. With increasing Sb concentration, the optical energy gap increases gradually from 3.84 eV for undoped SnO<sub>2</sub> to 4.35 eV for 5.0 at. % Sb. After considering the Urbach tailing phenomenon as well as the Moss–Burstein effect, this increase was attributed to the increase in Moss–Burstein energy due to increased charge carrier concentration. Our study revealed that the film doped with 2.0 at. % Sb has the best optoelectronic properties, with a figure of merit of 4.18 (Ω/<em>cm</em><sup>2</sup>)<sup>−1</sup>.</div></div>","PeriodicalId":22081,"journal":{"name":"Surfaces and Interfaces","volume":"55 ","pages":"Article 105327"},"PeriodicalIF":5.7,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142552306","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-28DOI: 10.1016/j.surfin.2024.105349
Qiang Liu , Jingnan Wang , Yongan Yang , Xi Wang
Urea (NH2CONH2), a crucial nitrogen fertilizer and industrial raw material, is typically synthesized under rigorous reaction conditions. Currently, the electrocatalytic transformation of N2 and CO2 into urea is a promising strategy. However, finding a high-selectivity and high-activity catalyst remains a significant challenge. Herein, the activity of a series of transition metal clusters (VIII and IB groups) on copper-based catalysts for electrochemical coupling of CO2 and N2 has been systematically studied to produce urea via density functional theory (DFT). Most catalysts exhibit good thermodynamic stability and accomplish co-adsorb CO2 and N2. Notably, Fe3 and Ni3/Cu100 catalysts achieve C-N coupling via *CO and *N2, whereas Ru3, Rh3, Os3, and Ir3/Cu100 catalysts accomplish C-N coupling via *CO and *NHNH. Among all catalysts, the Ni3/Cu100 catalyst features excellent catalytic activity with a rate-determining step as low as 0.480 eV, and its C-N coupling only needs to overcome a barrier of 0.844 eV. Additionally, the Ni3/Cu100 catalyst can effectively inhibit the hydrogen evolution reaction (HER), further protonation of *CO and ammonia formation, thereby ensuring high selectivity for urea. Electronic structures analysis further reveals an “acceptance-donation” mechanism for the activation of *CO2 and *N2, with the introduction of the Ni3 cluster showing a decisive role. Therefore, this study may establish the foundation for the electrochemical synthesis of urea.
{"title":"The electrochemical synthesis of urea on triatomic cluster/Cu catalysts: A theoretical study","authors":"Qiang Liu , Jingnan Wang , Yongan Yang , Xi Wang","doi":"10.1016/j.surfin.2024.105349","DOIUrl":"10.1016/j.surfin.2024.105349","url":null,"abstract":"<div><div>Urea (NH<sub>2</sub>CONH<sub>2</sub>), a crucial nitrogen fertilizer and industrial raw material, is typically synthesized under rigorous reaction conditions. Currently, the electrocatalytic transformation of N<sub>2</sub> and CO<sub>2</sub> into urea is a promising strategy. However, finding a high-selectivity and high-activity catalyst remains a significant challenge. Herein, the activity of a series of transition metal clusters (VIII and IB groups) on copper-based catalysts for electrochemical coupling of CO<sub>2</sub> and N<sub>2</sub> has been systematically studied to produce urea via density functional theory (DFT). Most catalysts exhibit good thermodynamic stability and accomplish co-adsorb CO<sub>2</sub> and N<sub>2</sub>. Notably, Fe3 and Ni3/Cu100 catalysts achieve C-N coupling via *CO and *N<sub>2</sub>, whereas Ru3, Rh3, Os3, and Ir3/Cu100 catalysts accomplish C-N coupling via *CO and *NHNH. Among all catalysts, the Ni3/Cu100 catalyst features excellent catalytic activity with a rate-determining step as low as 0.480 eV, and its C-N coupling only needs to overcome a barrier of 0.844 eV. Additionally, the Ni3/Cu100 catalyst can effectively inhibit the hydrogen evolution reaction (HER), further protonation of *CO and ammonia formation, thereby ensuring high selectivity for urea. Electronic structures analysis further reveals an “acceptance-donation” mechanism for the activation of *CO<sub>2</sub> and *N<sub>2</sub>, with the introduction of the Ni3 cluster showing a decisive role. Therefore, this study may establish the foundation for the electrochemical synthesis of urea.</div></div>","PeriodicalId":22081,"journal":{"name":"Surfaces and Interfaces","volume":"55 ","pages":"Article 105349"},"PeriodicalIF":5.7,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142552359","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-28DOI: 10.1016/j.surfin.2024.105347
Weining Li , Xiaping Lu , Jiakang Li , Yingchun Yan , Junfeng Li , Kun Chen , Aijun Guo , He Liu , Dong Liu
Heteroatom-doped porous carbon materials are highly favored as catalysts for activating persulfates in the oxidative degradation of organic pollutants due to their low metal leaching risk and cost-effectiveness. Nonetheless, the complex process of creating heteroatom-doped carbon materials often results in suboptimal doping effects. This study uses N,P-enriched plants (Eichhornia crassipes after being used for nutrient-rich water remediation) as a raw material to prepare N-P co-doped catalysts in a single step. We thoroughly investigated their performance and mechanisms in dye degradation. The findings demonstrated that the adsorbent, with its rich pore structures, surface chemical functional groups, and graphite defect structures, could completely degrade a 100 mg L−1 MB solution within 20 min. Free radical quenching experiments and EPR analysis confirmed the presence of •OH, SO4•—, O2•— and 1O2, verifying their oxidative contributions. Moreover, it was determined that the non-radical pathway (1O2 oxidation) primarily drives the oxidative degradation in this system. Additionally, tests using a small-scale fixed-bed reactor and interference resistance highlighted the practical application potential of the adsorbent developed in this study. This study not only offers a dual solution for tackling nutrient enrichment and organic pollution in water bodies but also introduces a straightforward method for preparing N, P co-doped catalysts, significantly benefiting environmental protection.
{"title":"Rapid preparation of N,P co-doped carbon for advanced oxidative degradation of wastewater","authors":"Weining Li , Xiaping Lu , Jiakang Li , Yingchun Yan , Junfeng Li , Kun Chen , Aijun Guo , He Liu , Dong Liu","doi":"10.1016/j.surfin.2024.105347","DOIUrl":"10.1016/j.surfin.2024.105347","url":null,"abstract":"<div><div>Heteroatom-doped porous carbon materials are highly favored as catalysts for activating persulfates in the oxidative degradation of organic pollutants due to their low metal leaching risk and cost-effectiveness. Nonetheless, the complex process of creating heteroatom-doped carbon materials often results in suboptimal doping effects. This study uses N,P-enriched plants (Eichhornia crassipes after being used for nutrient-rich water remediation) as a raw material to prepare N-P co-doped catalysts in a single step. We thoroughly investigated their performance and mechanisms in dye degradation. The findings demonstrated that the adsorbent, with its rich pore structures, surface chemical functional groups, and graphite defect structures, could completely degrade a 100 mg L<sup>−1</sup> MB solution within 20 min. Free radical quenching experiments and EPR analysis confirmed the presence of •OH, SO<sub>4</sub><sup>•—</sup>, O<sub>2</sub><sup>•—</sup> and <sup>1</sup>O<sub>2</sub>, verifying their oxidative contributions. Moreover, it was determined that the non-radical pathway (<sup>1</sup>O<sub>2</sub> oxidation) primarily drives the oxidative degradation in this system. Additionally, tests using a small-scale fixed-bed reactor and interference resistance highlighted the practical application potential of the adsorbent developed in this study. This study not only offers a dual solution for tackling nutrient enrichment and organic pollution in water bodies but also introduces a straightforward method for preparing N, P co-doped catalysts, significantly benefiting environmental protection.</div></div>","PeriodicalId":22081,"journal":{"name":"Surfaces and Interfaces","volume":"55 ","pages":"Article 105347"},"PeriodicalIF":5.7,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142594132","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Inspired by the natural water harvesting mechanisms of desert beetles, cactus thorns, and leaf veins, we designed a heterogeneous wettability surface with superhydrophilic pattern integrating leaf vein as the directional water transport main channel, attached capillary triangles as auxiliary channel plus a deep rough desorption channel on an overall superhydrophobic surface for an efficient water collection. A superhydrophilic surface was initially fabricated on the stainless steel disc by laser marker ablation allowing 1 μL droplet to spread completely to 0° within 0.12 s, followed by fluorine-containing coating transforming superhydrophilic surface to superhydrophobic one. Directional water transport patterns were then etched on the superhydrophobic surfaces by the secondary laser marker. The surface energy gradient and Laplace pressure induced by the pattern facilitated directional fast transport and efficient desorption of droplets, thus improving water collection efficiency. The enhancement mechanism of the water harvesting behavior for such surfaces was analyzed, with one focus on enhancing collection in hydrophobic regions with capillaries to reduce bouncing off loss and the other on improving balanced cycling of the collection process. At a fog flow rate of 1500 ml/h and 20 cm away from the fog outlet, the directional leaf vein-patterned 19.625 cm2 sized surface demonstrated a fog water collection rate (WCR) of 5.6 Kg·m-2·h-1 and first drop collection at the 49th s, an impressively short time rarely reported. Compared to the superhydrophobic, superhydrophilic samples, and the reference, WCR increased by 180 %, 62 %, and 59 %, respectively, and the first droplet collection time decreased by 73 %, 46 %, and 62 %, respectively. This efficient water collection method has huge potential in arid regions.
{"title":"Water collection through a directional leaf vein pattern by fast laser marker ablation of stainless-steel","authors":"Hongtao Cui, Xiaolong Fang, Xiaowen Qi, Chengling Liu, Youfu Wang, Xiangfu Chen, Chenrui Wang","doi":"10.1016/j.surfin.2024.105332","DOIUrl":"10.1016/j.surfin.2024.105332","url":null,"abstract":"<div><div>Inspired by the natural water harvesting mechanisms of desert beetles, cactus thorns, and leaf veins, we designed a heterogeneous wettability surface with superhydrophilic pattern integrating leaf vein as the directional water transport main channel, attached capillary triangles as auxiliary channel plus a deep rough desorption channel on an overall superhydrophobic surface for an efficient water collection. A superhydrophilic surface was initially fabricated on the stainless steel disc by laser marker ablation allowing 1 μL droplet to spread completely to 0° within 0.12 s, followed by fluorine-containing coating transforming superhydrophilic surface to superhydrophobic one. Directional water transport patterns were then etched on the superhydrophobic surfaces by the secondary laser marker. The surface energy gradient and Laplace pressure induced by the pattern facilitated directional fast transport and efficient desorption of droplets, thus improving water collection efficiency. The enhancement mechanism of the water harvesting behavior for such surfaces was analyzed, with one focus on enhancing collection in hydrophobic regions with capillaries to reduce bouncing off loss and the other on improving balanced cycling of the collection process. At a fog flow rate of 1500 ml/h and 20 cm away from the fog outlet, the directional leaf vein-patterned 19.625 cm<sup>2</sup> sized surface demonstrated a fog water collection rate (WCR) of 5.6 Kg·m<sup>-2</sup>·h<sup>-1</sup> and first drop collection at the 49th s, an impressively short time rarely reported. Compared to the superhydrophobic, superhydrophilic samples, and the reference, WCR increased by 180 %, 62 %, and 59 %, respectively, and the first droplet collection time decreased by 73 %, 46 %, and 62 %, respectively. This efficient water collection method has huge potential in arid regions.</div></div>","PeriodicalId":22081,"journal":{"name":"Surfaces and Interfaces","volume":"55 ","pages":"Article 105332"},"PeriodicalIF":5.7,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142552302","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-28DOI: 10.1016/j.surfin.2024.105359
Jiyuan Sun, Ziqiang Chen, Linfeng Yuan, Junyan Xiang, Wentao Wang
Graphene is an ideal material for flexible sensors with outstanding stretchability and extensibility, but its further development is being severely hindered by the existing multi-step routes. Laser-induced graphene (LIG) is a recently emerging technology that enables industrial scale preparation with mask-free, fast-scanning speed, and high spatial resolution. In this review, the latest advances on three-dimensional porous LIG from the perspective of precursor selections to manufacturing methods are presented. First, the commonly precursors such as graphene oxide, polymers, and natural materials for photothermal/chemical transformation was classified in combined with auxiliary processing equipment. Then, three all-purpose fabrication strategies, including casting-and-peeling transfer, topology architecture and Kirigami design, are summarized for the LIG-based sensors. Next, the representative progress of flexible/stretchable LIG-based pressure, strain, liquid, and gas sensors were categorized based on sensing principles, with the aim of improving the sensing performance in practical applications. Finally, the newest developments, major challenges, and outlook in LIG-manufacturing and integrated flexible sensors are discussed, showing huge potential in future wearable electronics.
石墨烯是柔性传感器的理想材料，具有出色的拉伸性和延伸性，但现有的多步骤制备方法严重阻碍了石墨烯的进一步发展。激光诱导石墨烯（LIG）是最近兴起的一种技术，可实现无掩膜、快速扫描和高空间分辨率的工业规模制备。本综述从前驱体选择到制造方法的角度，介绍了三维多孔石墨烯的最新进展。首先，结合辅助加工设备对氧化石墨烯、聚合物、光热/化学转化天然材料等常用前驱体进行了分类。然后，总结了基于 LIG 的传感器的三种通用制造策略，包括浇铸-剥离转移、拓扑结构和 Kirigami 设计。接着，根据传感原理对基于 LIG 的柔性/可拉伸压力、应变、液体和气体传感器的代表性进展进行了分类，旨在提高实际应用中的传感性能。最后，讨论了 LIG 制造和集成柔性传感器的最新发展、主要挑战和前景，展示了未来可穿戴电子产品的巨大潜力。
{"title":"Recent advances in flexible/stretchable sensors using laser-induced three-dimensional porous graphene: From precursor to manufacturing","authors":"Jiyuan Sun, Ziqiang Chen, Linfeng Yuan, Junyan Xiang, Wentao Wang","doi":"10.1016/j.surfin.2024.105359","DOIUrl":"10.1016/j.surfin.2024.105359","url":null,"abstract":"<div><div>Graphene is an ideal material for flexible sensors with outstanding stretchability and extensibility, but its further development is being severely hindered by the existing multi-step routes. Laser-induced graphene (LIG) is a recently emerging technology that enables industrial scale preparation with mask-free, fast-scanning speed, and high spatial resolution. In this review, the latest advances on three-dimensional porous LIG from the perspective of precursor selections to manufacturing methods are presented. First, the commonly precursors such as graphene oxide, polymers, and natural materials for photothermal/chemical transformation was classified in combined with auxiliary processing equipment. Then, three all-purpose fabrication strategies, including casting-and-peeling transfer, topology architecture and Kirigami design, are summarized for the LIG-based sensors. Next, the representative progress of flexible/stretchable LIG-based pressure, strain, liquid, and gas sensors were categorized based on sensing principles, with the aim of improving the sensing performance in practical applications. Finally, the newest developments, major challenges, and outlook in LIG-manufacturing and integrated flexible sensors are discussed, showing huge potential in future wearable electronics.</div></div>","PeriodicalId":22081,"journal":{"name":"Surfaces and Interfaces","volume":"55 ","pages":"Article 105359"},"PeriodicalIF":5.7,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142552021","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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