Jamal Attarki, Malika Khnifira, Wafaa Boumya, Hind Hajjaoui, Anas Mahsoune, M’hamed Sadiq, Mounia Achak, Noureddine Barka, Mohamed Abdennouri
The research purpose of this work is to examine the adsorption interaction of gaseous molecules (GMs), such as NO, NO2, SO, SO2, and SO3, with the surface of sodium magnesium phosphate NaMgPO4 (033), in a neutral medium, using two different computational methods: density functional theory (DFT) and Monte Carlo dynamic simulation (MCDS). Various quantum and dynamic descriptors, such as global and local quantum descriptors and the radial distribution function (RDF), are also evaluated and discussed. The data obtained revealed that the NO2 molecule has a small energy gap (0.363 eV) when compared to the other molecules, which means that it is highly reactive and is liable to adsorb, or stick, to the surface of NaMgPO4 (033). Furthermore, this NO2 molecule exhibits good adsorption in aqueous media, returning to the lowest global hardness value (0.1815 eV). MCDS predicted adsorption energies of −874.03, −819.94, −924.81, −876.33, and −977.71 kcal/mol for NO, NO2, SO, SO2, and SO3, respectively. These energies are negative, implying that adsorption occurs spontaneously. Thus, the side views indicated which SO, NO, and SO3 molecules are adsorbed in parallel to NaMgPO4 and the other SO2 and NO2 molecules are adsorbed horizontally. Eventually, the theoretical results reveal that the studied gaseous molecules interact strongly with NaMgPO4. The result obtained by radial distribution function (RDF) analysis for all complexes below 3.5 Å confirm that the adsorption is of the chemi1cal type.
{"title":"DFT and MCDS Outcome for a Comparative Analysis of NO, NO2, SO, SO2 and SO3 Gas Adsorption onto a NaMgPO4 (033) Surface","authors":"Jamal Attarki, Malika Khnifira, Wafaa Boumya, Hind Hajjaoui, Anas Mahsoune, M’hamed Sadiq, Mounia Achak, Noureddine Barka, Mohamed Abdennouri","doi":"10.3390/surfaces6040030","DOIUrl":"https://doi.org/10.3390/surfaces6040030","url":null,"abstract":"The research purpose of this work is to examine the adsorption interaction of gaseous molecules (GMs), such as NO, NO2, SO, SO2, and SO3, with the surface of sodium magnesium phosphate NaMgPO4 (033), in a neutral medium, using two different computational methods: density functional theory (DFT) and Monte Carlo dynamic simulation (MCDS). Various quantum and dynamic descriptors, such as global and local quantum descriptors and the radial distribution function (RDF), are also evaluated and discussed. The data obtained revealed that the NO2 molecule has a small energy gap (0.363 eV) when compared to the other molecules, which means that it is highly reactive and is liable to adsorb, or stick, to the surface of NaMgPO4 (033). Furthermore, this NO2 molecule exhibits good adsorption in aqueous media, returning to the lowest global hardness value (0.1815 eV). MCDS predicted adsorption energies of −874.03, −819.94, −924.81, −876.33, and −977.71 kcal/mol for NO, NO2, SO, SO2, and SO3, respectively. These energies are negative, implying that adsorption occurs spontaneously. Thus, the side views indicated which SO, NO, and SO3 molecules are adsorbed in parallel to NaMgPO4 and the other SO2 and NO2 molecules are adsorbed horizontally. Eventually, the theoretical results reveal that the studied gaseous molecules interact strongly with NaMgPO4. The result obtained by radial distribution function (RDF) analysis for all complexes below 3.5 Å confirm that the adsorption is of the chemi1cal type.","PeriodicalId":22129,"journal":{"name":"Surfaces","volume":"40 7","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"136348336","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}
Samia A. Kosa, Amna N. Khan, Basma Al-Johani, L. A. Taib, M. Aslam, Wafa A. Bawazir, A. Hameed, M. Tahir Soomro
To realize simple and intelligent electrochemical ammonia (NH3) detection in water, highly dense colloidal copper nanoparticles (CuNPs) were prepared and subsequently deposited onto a glassy carbon electrode (GCE). The CuNPs/GCE was then placed in an oven at 60 °C to intelligently transform CuNPs into cuprous oxide (Cu2O) thin film. The colloidal CuNPs were characterized by ultraviolet-visible (UV-Vis) spectroscopy, whereas the fabricated Cu2O/GCE was subjected to Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and electrochemical impedance spectroscopy (EIS). The XRD of Cu2O/GCE showed the crystalline nature of the thermally converted Cu2O thin film, whereas XPS demonstrated that the thin film formed on the surface of GCE was primarily composed of Cu2O. The SEM images of Cu2O/GCE revealed Cu2O crystals with hexapod morphology. The EIS study exhibited substantially higher charger transfer activity of Cu2O/GCE compared to bare GCE. The drop coating of ammonia (NH3) solution onto Cu2O/GCE enabled the fabricated electrode to be utilized as an electrochemical sensor for NH3 detection in water. The cyclic voltammetric (CV) behavior of NH3/Cu2O/GCE was investigated in 0.1 M pH 7 phosphate buffer, which led to the formation of a copper-ammonia complex and revealed the nobility of the fabricated electrode. The square wave voltammetric (SWV) response was linear over the 10 µM and 1000 µM ranges with a detection limit of 6.23 µM and good reproducibility. The NH3/Cu2O/GCE displayed high selectivity for the detection of NH3 in the presence of various coexisting cations and anions in 0.1 M pH 7 phosphate buffer. The recovery of NH3 in the drinking water sample varied from 98.2% to 99.1%.
为了实现水中氨(NH3)的简单智能电化学检测，制备了高密度胶体铜纳米粒子(CuNPs)，并将其沉积在玻碳电极(GCE)上。然后将CuNPs/GCE置于60℃的烤箱中，将CuNPs智能地转化为氧化亚铜(Cu2O)薄膜。采用紫外-可见(UV-Vis)光谱对胶体Cu2O/GCE进行了表征，采用傅里叶变换红外光谱(FTIR)、x射线衍射(XRD)、x射线光电子能谱(XPS)、扫描电镜(SEM)和电化学阻抗谱(EIS)对制备的Cu2O/GCE进行了表征。Cu2O/GCE的XRD表征了热转化Cu2O薄膜的结晶性质，而XPS表征了GCE表面形成的薄膜主要由Cu2O组成。Cu2O/GCE的SEM图像显示Cu2O晶体具有六足体形态。EIS研究显示，与纯GCE相比，Cu2O/GCE的充电器转移活性明显更高。氨(NH3)溶液滴涂在Cu2O/GCE上，使制备的电极可作为水中NH3检测的电化学传感器。研究了NH3/Cu2O/GCE在0.1 M pH 7磷酸盐缓冲液中的循环伏安(CV)行为，发现铜-氨络合物的形成，揭示了所制备电极的高级性。方波伏安(SWV)响应在10µM和1000µM范围内呈线性，检出限为6.23µM，重现性好。在0.1 M pH 7的磷酸盐缓冲液中，NH3/Cu2O/GCE对不同阳离子和阴离子共存的NH3具有较高的选择性。饮用水样品中NH3的回收率为98.2% ~ 99.1%。
{"title":"Simple and Intelligent Electrochemical Detection of Ammonia over Cuprous Oxide Thin Film Electrode","authors":"Samia A. Kosa, Amna N. Khan, Basma Al-Johani, L. A. Taib, M. Aslam, Wafa A. Bawazir, A. Hameed, M. Tahir Soomro","doi":"10.3390/surfaces6040029","DOIUrl":"https://doi.org/10.3390/surfaces6040029","url":null,"abstract":"To realize simple and intelligent electrochemical ammonia (NH3) detection in water, highly dense colloidal copper nanoparticles (CuNPs) were prepared and subsequently deposited onto a glassy carbon electrode (GCE). The CuNPs/GCE was then placed in an oven at 60 °C to intelligently transform CuNPs into cuprous oxide (Cu2O) thin film. The colloidal CuNPs were characterized by ultraviolet-visible (UV-Vis) spectroscopy, whereas the fabricated Cu2O/GCE was subjected to Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and electrochemical impedance spectroscopy (EIS). The XRD of Cu2O/GCE showed the crystalline nature of the thermally converted Cu2O thin film, whereas XPS demonstrated that the thin film formed on the surface of GCE was primarily composed of Cu2O. The SEM images of Cu2O/GCE revealed Cu2O crystals with hexapod morphology. The EIS study exhibited substantially higher charger transfer activity of Cu2O/GCE compared to bare GCE. The drop coating of ammonia (NH3) solution onto Cu2O/GCE enabled the fabricated electrode to be utilized as an electrochemical sensor for NH3 detection in water. The cyclic voltammetric (CV) behavior of NH3/Cu2O/GCE was investigated in 0.1 M pH 7 phosphate buffer, which led to the formation of a copper-ammonia complex and revealed the nobility of the fabricated electrode. The square wave voltammetric (SWV) response was linear over the 10 µM and 1000 µM ranges with a detection limit of 6.23 µM and good reproducibility. The NH3/Cu2O/GCE displayed high selectivity for the detection of NH3 in the presence of various coexisting cations and anions in 0.1 M pH 7 phosphate buffer. The recovery of NH3 in the drinking water sample varied from 98.2% to 99.1%.","PeriodicalId":22129,"journal":{"name":"Surfaces","volume":"10 3","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135590150","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}
Omar H. Abd-Elkader, Mai Nasrallah, Lotfi Aleya, Mohamed Nasrallah
Employing a self-combustion method supported by egg white, pure and Fe-doped ZnO/C nanoparticles successfully biosynthesized. XRD, FTIR, Raman, SEM/EDS and TEM measurements were used to characterize the pure and doped systems. The materials under investigation’s optical, surface and magnetic characteristics were recognized. Only one zinc oxide crystalline phase exhibiting a hexagonal shape comparable to wurtzite was present in the systems of pure and Fe-doped ZnO/C. Due to the variation in ionic radii, doping ZnO/C system with iron ions resulted in a decrease in unit cell volume; it revealed that ions of iron had been integrated into the lattice of zinc oxides. FTIR analysis shows characteristic vibration modes related to ZnO and that of carbon groups, confirming the formation of the ZnO/C system. In a perfect match with the IR data, which represent two bands at 1120 and 1399 cm−1 attributed to carbon groups, the Raman analysis shows that in the freshly manufactured materials, sp2 and disordered G and D carbon bands have both graphitized. Fe-doping of the ZnO/C system with different amounts of iron ions resulted in the change in the size and agglomeration of the particle’s system. The doped ZnO/C system has a surface area smaller than that of the pure system due to the decrease in both the mean pore radius and the total pore volume. Doping the ZnO/C system with 2 and 5 mol% Fe2O3 resulted in optical band gaps expanding from 3.17 eV to 3.27 eV and 3.57 eV, respectively. Due to the doping with iron ions, a magnetic transition from a fully diamagnetic state to a slightly ferromagnetic state was detected.
{"title":"Biosynthesis, Optical and Magnetic Properties of Fe-Doped ZnO/C Nanoparticles","authors":"Omar H. Abd-Elkader, Mai Nasrallah, Lotfi Aleya, Mohamed Nasrallah","doi":"10.3390/surfaces6040028","DOIUrl":"https://doi.org/10.3390/surfaces6040028","url":null,"abstract":"Employing a self-combustion method supported by egg white, pure and Fe-doped ZnO/C nanoparticles successfully biosynthesized. XRD, FTIR, Raman, SEM/EDS and TEM measurements were used to characterize the pure and doped systems. The materials under investigation’s optical, surface and magnetic characteristics were recognized. Only one zinc oxide crystalline phase exhibiting a hexagonal shape comparable to wurtzite was present in the systems of pure and Fe-doped ZnO/C. Due to the variation in ionic radii, doping ZnO/C system with iron ions resulted in a decrease in unit cell volume; it revealed that ions of iron had been integrated into the lattice of zinc oxides. FTIR analysis shows characteristic vibration modes related to ZnO and that of carbon groups, confirming the formation of the ZnO/C system. In a perfect match with the IR data, which represent two bands at 1120 and 1399 cm−1 attributed to carbon groups, the Raman analysis shows that in the freshly manufactured materials, sp2 and disordered G and D carbon bands have both graphitized. Fe-doping of the ZnO/C system with different amounts of iron ions resulted in the change in the size and agglomeration of the particle’s system. The doped ZnO/C system has a surface area smaller than that of the pure system due to the decrease in both the mean pore radius and the total pore volume. Doping the ZnO/C system with 2 and 5 mol% Fe2O3 resulted in optical band gaps expanding from 3.17 eV to 3.27 eV and 3.57 eV, respectively. Due to the doping with iron ions, a magnetic transition from a fully diamagnetic state to a slightly ferromagnetic state was detected.","PeriodicalId":22129,"journal":{"name":"Surfaces","volume":"18 3","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135315884","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}
Prabu Baskar, Shalini Annadurai, Sushmithaa Panneerselvam, Mayakrishnan Prabakaran, Jongpil Kim
Researchers have just discovered an alternative to synthetic corrosion inhibitors, which are hazardous and terrible for the ecosystem, to prevent rusting in the environment. A metal corrodes when it is subjected to corrosive media (acid, base, or saline) and they deteriorate, leading to failure. The most straightforward and affordable corrosion protection and prevention technique in acidic environments has been proven to be corrosion inhibitors. On industrial surfaces, pieces of machinery, or vessels, these inhibitors slow the rate of corrosion, preventing the monetary losses brought on by metallic corrosion. Recently, attention has been directed to developing ecologically appropriate corrosion retardation methods because inorganic and organic inhibitors are harmful and expensive. Recent studies have focused on green mild steel (MS) corrosion inhibitors that mimic industrial processes in acidic conditions. This presentation briefly covers the many types of corrosion, the corrosion process and the most recent studies on using natural plant extracts as corrosion inhibitors. Since they are safe and cost-effective, green corrosion inhibitors are a new trend in preventing corrosion. These inhibitors are produced from various plant parts, and inhibition efficiency (IE) also depends on them. To ascertain the IE of the corrosion inhibitor, some experiments, including computational studies (quantum calculations and MD simulations), electrochemical measurements (electrochemical impedance (EIS) and potentio-dynamic polarization), surface morphology atomic force microscopy (AFM), scanning electron microscopy (SEM)/energy-dispersive X-ray analysis (EDX) and UV–visible spectroscopy are carried out. It has been demonstrated that the IE is maximum for green corrosion inhibitors compared to synthetic inhibitors. This paper provides an overview of the properties, mechanism of corrosion inhibitors, nature of green corrosion inhibitors and their IE obtained by performing tests. This review article discussion shows that reinforcement with plant extract performs well in aggressive environments, which is evident from electrochemical studies and surface analysis when compared to reinforcement with inhibitors.
{"title":"An Outline of Employing Metals and Alloys in Corrosive Settings with Ecologically Acceptable Corrosion Inhibitors","authors":"Prabu Baskar, Shalini Annadurai, Sushmithaa Panneerselvam, Mayakrishnan Prabakaran, Jongpil Kim","doi":"10.3390/surfaces6040027","DOIUrl":"https://doi.org/10.3390/surfaces6040027","url":null,"abstract":"Researchers have just discovered an alternative to synthetic corrosion inhibitors, which are hazardous and terrible for the ecosystem, to prevent rusting in the environment. A metal corrodes when it is subjected to corrosive media (acid, base, or saline) and they deteriorate, leading to failure. The most straightforward and affordable corrosion protection and prevention technique in acidic environments has been proven to be corrosion inhibitors. On industrial surfaces, pieces of machinery, or vessels, these inhibitors slow the rate of corrosion, preventing the monetary losses brought on by metallic corrosion. Recently, attention has been directed to developing ecologically appropriate corrosion retardation methods because inorganic and organic inhibitors are harmful and expensive. Recent studies have focused on green mild steel (MS) corrosion inhibitors that mimic industrial processes in acidic conditions. This presentation briefly covers the many types of corrosion, the corrosion process and the most recent studies on using natural plant extracts as corrosion inhibitors. Since they are safe and cost-effective, green corrosion inhibitors are a new trend in preventing corrosion. These inhibitors are produced from various plant parts, and inhibition efficiency (IE) also depends on them. To ascertain the IE of the corrosion inhibitor, some experiments, including computational studies (quantum calculations and MD simulations), electrochemical measurements (electrochemical impedance (EIS) and potentio-dynamic polarization), surface morphology atomic force microscopy (AFM), scanning electron microscopy (SEM)/energy-dispersive X-ray analysis (EDX) and UV–visible spectroscopy are carried out. It has been demonstrated that the IE is maximum for green corrosion inhibitors compared to synthetic inhibitors. This paper provides an overview of the properties, mechanism of corrosion inhibitors, nature of green corrosion inhibitors and their IE obtained by performing tests. This review article discussion shows that reinforcement with plant extract performs well in aggressive environments, which is evident from electrochemical studies and surface analysis when compared to reinforcement with inhibitors.","PeriodicalId":22129,"journal":{"name":"Surfaces","volume":"24 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"136210434","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}
Oxide films produced from plasma electrolytic oxidation are porous in structure. While they have some passivating effect in Mg alloys, the pores still lead to corrosion over long periods of exposure. In this study, spray pyrolysis was used to seal the porous oxide layer developed through the plasma electrolytic oxidation method on Mg alloy AZ31. The PEO coating acted as a good base for the application of spray pyrolysis due to its morphology. Three different kinds of coatings were obtained using different precursors: zinc acetate for ZnO, phosphoric acid for phosphate (P), and a mixture of zinc acetate and sodium phosphate for ZnO+P. The corrosion performance of all three coatings was studied by performing electrochemical impedance and polarization tests on the samples. Mass loss over a duration of 1 week was measured in 3% NaCl solution using immersion gravimetry. The coating with only phosphate (P) was found to be most corrosion-resistant with 52 times lower rate of corrosion and 50 times more polarization potential. The chemical composition of the corrosion products was studied using XRD and SEM-EDS analysis. Mass loss in ZnO+P was the highest, at up to 1.4 and 5.1 times higher than ZnO and P, respectively.
{"title":"Combined PEO and Spray Pyrolysis Coatings of Phosphate and ZnO for Enhancing Corrosion Resistance in AZ31 Mg Alloy","authors":"Ashish Kumar Singh, Reinis Drunka, Paula Iesalniece, Ilmars Blumbergs, Ints Steins, Toms-Valdemars Eiduks, Mairis Iesalnieks, Konstantins Savkovs","doi":"10.3390/surfaces6040026","DOIUrl":"https://doi.org/10.3390/surfaces6040026","url":null,"abstract":"Oxide films produced from plasma electrolytic oxidation are porous in structure. While they have some passivating effect in Mg alloys, the pores still lead to corrosion over long periods of exposure. In this study, spray pyrolysis was used to seal the porous oxide layer developed through the plasma electrolytic oxidation method on Mg alloy AZ31. The PEO coating acted as a good base for the application of spray pyrolysis due to its morphology. Three different kinds of coatings were obtained using different precursors: zinc acetate for ZnO, phosphoric acid for phosphate (P), and a mixture of zinc acetate and sodium phosphate for ZnO+P. The corrosion performance of all three coatings was studied by performing electrochemical impedance and polarization tests on the samples. Mass loss over a duration of 1 week was measured in 3% NaCl solution using immersion gravimetry. The coating with only phosphate (P) was found to be most corrosion-resistant with 52 times lower rate of corrosion and 50 times more polarization potential. The chemical composition of the corrosion products was studied using XRD and SEM-EDS analysis. Mass loss in ZnO+P was the highest, at up to 1.4 and 5.1 times higher than ZnO and P, respectively.","PeriodicalId":22129,"journal":{"name":"Surfaces","volume":"31 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"136356575","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}
Amir Ghiami, Annika Grundmann, Songyao Tang, Hleb Fiadziushkin, Zhaodong Wang, Stephan Aussen, Susanne Hoffmann-Eifert, Michael Heuken, Holger Kalisch, Andrei Vescan
Metal–organic chemical vapor deposition (MOCVD) is a key method for scalable synthesis of two-dimensional transition metal dichalcogenide (2D-TMDC) layers. However, it faces several challenges, such as the unintentional co-deposition of carbon impurities resulting from the pyrolysis of metal–organic precursors. This study investigates the chemical features of carbon and its impact on the photoluminescence property and air stability of 2D-MoS2. Using X-ray photoemission spectroscopy (XPS), it was found that the carbon impurities show characteristics similar to those of sp2-bonded graphitic carbon. Upon prolonged (20–40 weeks) exposure to the atmosphere, the incorporated carbon appears to react with 2D-MoS2, forming a MoS2−xCx solid solution. At the same time, a gradual decrease in the S/Mo ratio implies the formation of sulfur vacancies was also observed. These two processes lead to crystal degradation over time, as evidenced by the gradual quenching of the Raman and photoluminescence (PL) peaks. More detailed PL analyses suggest a charge transfer mechanism between sp2-carbon/2D-MoS2 and 2D-MoS2/air-adsorbates, which, in the short term, could alter PL emissions and appear to further intensify the degradation of 2D-MoS2 in the long-term. The findings highlight the strong impact of unintentionally co-deposited carbon on the optical properties and air stability of MOCVD 2D-MoS2 layers.
{"title":"Impact of Carbon Impurities on Air Stability of MOCVD 2D-MoS2","authors":"Amir Ghiami, Annika Grundmann, Songyao Tang, Hleb Fiadziushkin, Zhaodong Wang, Stephan Aussen, Susanne Hoffmann-Eifert, Michael Heuken, Holger Kalisch, Andrei Vescan","doi":"10.3390/surfaces6040025","DOIUrl":"https://doi.org/10.3390/surfaces6040025","url":null,"abstract":"Metal–organic chemical vapor deposition (MOCVD) is a key method for scalable synthesis of two-dimensional transition metal dichalcogenide (2D-TMDC) layers. However, it faces several challenges, such as the unintentional co-deposition of carbon impurities resulting from the pyrolysis of metal–organic precursors. This study investigates the chemical features of carbon and its impact on the photoluminescence property and air stability of 2D-MoS2. Using X-ray photoemission spectroscopy (XPS), it was found that the carbon impurities show characteristics similar to those of sp2-bonded graphitic carbon. Upon prolonged (20–40 weeks) exposure to the atmosphere, the incorporated carbon appears to react with 2D-MoS2, forming a MoS2−xCx solid solution. At the same time, a gradual decrease in the S/Mo ratio implies the formation of sulfur vacancies was also observed. These two processes lead to crystal degradation over time, as evidenced by the gradual quenching of the Raman and photoluminescence (PL) peaks. More detailed PL analyses suggest a charge transfer mechanism between sp2-carbon/2D-MoS2 and 2D-MoS2/air-adsorbates, which, in the short term, could alter PL emissions and appear to further intensify the degradation of 2D-MoS2 in the long-term. The findings highlight the strong impact of unintentionally co-deposited carbon on the optical properties and air stability of MOCVD 2D-MoS2 layers.","PeriodicalId":22129,"journal":{"name":"Surfaces","volume":"52 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135300919","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}
Rodrigo M. Barros, Cínthia C. Bonatto, Marcelo H. S. Ramada, Luciano P. Silva
Advances in nanotechnology have contributed to many innovative approaches in the forensic sciences, including the development of new techniques and protocols for latent fingermark detection. Among other nanomaterials, metal-based nanoparticles have been explored as suitable developers for fingermarks present on surfaces that challenge traditionally established methods. The present study explored, for the first time in the forensic science literature, the application of greenly synthesized silver nanoparticles (AgNPs) for latent fingermark surface-assisted laser desorption/ionization mass spectrometry (SALDI MS) analysis. A leaf extract of a native plant from the Cerrado biome was used for green synthesis of the AgNPs, and their hydrodynamic diameter, polydispersity index (PdI), and Zeta potential values were evaluated. Latent fingermarks were produced by three distinct donors and treated with α-CHCA matrix or AgNP suspension and were further investigated using commercial matrix assisted laser desorption/ionization (MALDI)-TOF MS equipment in the m/z range of 100–1000. Characterization results of the AgNPs indicated an average hydrodynamic diameter of 25.94 ± 0.30 nm, a PdI of 0.659 ± 0.085, and a Zeta potential of −33.4 ± 2.6 mV. The silver ions detected showed a relative intensity at least 20× higher for greenly synthesized AgNPs than for AgNO3 suspension, which may be advantageous for the detection of molecular species, especially olefins, present in forensic traces. The AgNP-based SALDI MS approach for the analysis of latent fingermarks showed intense ions at m/z 106.9, 215.8, and 322.7, referring to silver cation species that have been reported as important internal calibrants. The detection of components from endogenous and exogenous sources in latent fingermarks was achieved using the present approach. Greenly synthesized AgNPs may offer a new cost-effective, eco-friendly, and easily scaled up method for application in the chemical analysis of fingermarks.
{"title":"Surface-Assisted Laser Desorption/Ionization Mass Spectrometry Analysis of Latent Fingermarks Using Greenly Synthesized Silver Nanoparticles","authors":"Rodrigo M. Barros, Cínthia C. Bonatto, Marcelo H. S. Ramada, Luciano P. Silva","doi":"10.3390/surfaces6040024","DOIUrl":"https://doi.org/10.3390/surfaces6040024","url":null,"abstract":"Advances in nanotechnology have contributed to many innovative approaches in the forensic sciences, including the development of new techniques and protocols for latent fingermark detection. Among other nanomaterials, metal-based nanoparticles have been explored as suitable developers for fingermarks present on surfaces that challenge traditionally established methods. The present study explored, for the first time in the forensic science literature, the application of greenly synthesized silver nanoparticles (AgNPs) for latent fingermark surface-assisted laser desorption/ionization mass spectrometry (SALDI MS) analysis. A leaf extract of a native plant from the Cerrado biome was used for green synthesis of the AgNPs, and their hydrodynamic diameter, polydispersity index (PdI), and Zeta potential values were evaluated. Latent fingermarks were produced by three distinct donors and treated with α-CHCA matrix or AgNP suspension and were further investigated using commercial matrix assisted laser desorption/ionization (MALDI)-TOF MS equipment in the m/z range of 100–1000. Characterization results of the AgNPs indicated an average hydrodynamic diameter of 25.94 ± 0.30 nm, a PdI of 0.659 ± 0.085, and a Zeta potential of −33.4 ± 2.6 mV. The silver ions detected showed a relative intensity at least 20× higher for greenly synthesized AgNPs than for AgNO3 suspension, which may be advantageous for the detection of molecular species, especially olefins, present in forensic traces. The AgNP-based SALDI MS approach for the analysis of latent fingermarks showed intense ions at m/z 106.9, 215.8, and 322.7, referring to silver cation species that have been reported as important internal calibrants. The detection of components from endogenous and exogenous sources in latent fingermarks was achieved using the present approach. Greenly synthesized AgNPs may offer a new cost-effective, eco-friendly, and easily scaled up method for application in the chemical analysis of fingermarks.","PeriodicalId":22129,"journal":{"name":"Surfaces","volume":"213 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135351055","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}
Porous carbon is an emerging material for the capture of CO2 from point sources of emissions due to its high structural, mechanical, and chemical stability, along with reusability advantages. Currently, research efforts are mainly focused on high- or medium-pressure adsorption, rather than low-pressure or DAC (direct air capture) conditions. Highly porous and functionalized carbon, containing heteroatoms (N, O, etc.), is synthesized using different activation synthesis routes, such as hard template, soft template, and chemical activation, to achieve high CO2 capture efficiency at various temperatures and pressure ranges. Fundamental pore formation mechanisms with different activation routes have been evaluated and explored. Higher porosity alone can be ineffective without the presence of proper saturated diffusion pathways for CO2 transfer. Therefore, it is imperative to emphasize more rational multi-hierarchical macro-/meso-/micro-/super-/ultra-pore design strategies to achieve a higher utilization efficiency of these pores. Moreover, the present research primarily focuses on powder-based hierarchical porous carbon materials, which may reduce the efficiency of the capture performance when shaping the powder into pellets or fixed-bed shapes for applications considered. Therefore, it is imperative to develop a synthesis strategy for pelletized porous carbon and to explore its mechanistic synthesis route and potential for CO2 capture.
{"title":"Porous Carbon for CO2 Capture Technology: Unveiling Fundamentals and Innovations","authors":"Gazi A. K. M. Rafiqul Bari, Jae-Ho Jeong","doi":"10.3390/surfaces6030023","DOIUrl":"https://doi.org/10.3390/surfaces6030023","url":null,"abstract":"Porous carbon is an emerging material for the capture of CO2 from point sources of emissions due to its high structural, mechanical, and chemical stability, along with reusability advantages. Currently, research efforts are mainly focused on high- or medium-pressure adsorption, rather than low-pressure or DAC (direct air capture) conditions. Highly porous and functionalized carbon, containing heteroatoms (N, O, etc.), is synthesized using different activation synthesis routes, such as hard template, soft template, and chemical activation, to achieve high CO2 capture efficiency at various temperatures and pressure ranges. Fundamental pore formation mechanisms with different activation routes have been evaluated and explored. Higher porosity alone can be ineffective without the presence of proper saturated diffusion pathways for CO2 transfer. Therefore, it is imperative to emphasize more rational multi-hierarchical macro-/meso-/micro-/super-/ultra-pore design strategies to achieve a higher utilization efficiency of these pores. Moreover, the present research primarily focuses on powder-based hierarchical porous carbon materials, which may reduce the efficiency of the capture performance when shaping the powder into pellets or fixed-bed shapes for applications considered. Therefore, it is imperative to develop a synthesis strategy for pelletized porous carbon and to explore its mechanistic synthesis route and potential for CO2 capture.","PeriodicalId":22129,"journal":{"name":"Surfaces","volume":"123 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135202744","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}
Bacterial adhesion and biofilm formation on the surface of titanium implants are the main causes of implant-associated infection. An antibacterial coating on the implant surface can reduce the risk of biofilm formation. The aim of this study was to investigate the bactericidal effects of a van-comycin-loaded polymer coated on an implant surface. For this purpose, poly(N-isopropylacrylamide) (PNIPAAm) was first synthesized as a homopolymer or by co-polymerization with acrylamide (PNIPAAm-AAm) at a 5% weight ratio. Then, thin and uniform polymer coatings were prepared using the spin coating technique. The degree of surface hydro-philicity of the polymer coatings was evaluated by measuring the water contact angle (CA). For the antibacterial tests, the polymer-coated surfaces were loaded with vancomycin. The tests were performed in three conditions: on a glass surface (control), on a PNIPAAm-AAm-coated surface, and on a PNIPAAm-AAm-coated surface loaded with vancomycin. The death rates of the bacteria in contact with the coated surfaces were evaluated at different temperatures with fluorescence microscopy. A scanning electron microscopy (SEM) analysis of cross sections of the polymer coatings revealed a uniform thin film of approximately 200 nm in thickness. The water contact angle analysis performed at different temperatures revealed that the polymer-coated surfaces were more hydrophobic (CAs ranging between 53° and 63°) than the uncoated glass surface (CA ranging between 15° and 35°). The bacterial death rate, measured at 40 °C or while continuously switching the temperature between 37 °C and 40 °C, was higher in the presence of the surface coated with vancomycin-loaded PNIPAAm-AAm than when using the other surfaces (p-value ≤ 0.001). The vancomycin-loaded polymer coating evaluated in this study exhibited effective antibacterial properties when the polymer reached the phase transition temperature.
{"title":"The Antibacterial Performance of Implant Coating Made of Vancomycin-Loaded Polymer Material: An In Vitro Study","authors":"Ali Alenezi","doi":"10.3390/surfaces6030022","DOIUrl":"https://doi.org/10.3390/surfaces6030022","url":null,"abstract":"Bacterial adhesion and biofilm formation on the surface of titanium implants are the main causes of implant-associated infection. An antibacterial coating on the implant surface can reduce the risk of biofilm formation. The aim of this study was to investigate the bactericidal effects of a van-comycin-loaded polymer coated on an implant surface. For this purpose, poly(N-isopropylacrylamide) (PNIPAAm) was first synthesized as a homopolymer or by co-polymerization with acrylamide (PNIPAAm-AAm) at a 5% weight ratio. Then, thin and uniform polymer coatings were prepared using the spin coating technique. The degree of surface hydro-philicity of the polymer coatings was evaluated by measuring the water contact angle (CA). For the antibacterial tests, the polymer-coated surfaces were loaded with vancomycin. The tests were performed in three conditions: on a glass surface (control), on a PNIPAAm-AAm-coated surface, and on a PNIPAAm-AAm-coated surface loaded with vancomycin. The death rates of the bacteria in contact with the coated surfaces were evaluated at different temperatures with fluorescence microscopy. A scanning electron microscopy (SEM) analysis of cross sections of the polymer coatings revealed a uniform thin film of approximately 200 nm in thickness. The water contact angle analysis performed at different temperatures revealed that the polymer-coated surfaces were more hydrophobic (CAs ranging between 53° and 63°) than the uncoated glass surface (CA ranging between 15° and 35°). The bacterial death rate, measured at 40 °C or while continuously switching the temperature between 37 °C and 40 °C, was higher in the presence of the surface coated with vancomycin-loaded PNIPAAm-AAm than when using the other surfaces (p-value ≤ 0.001). The vancomycin-loaded polymer coating evaluated in this study exhibited effective antibacterial properties when the polymer reached the phase transition temperature.","PeriodicalId":22129,"journal":{"name":"Surfaces","volume":"21 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135782289","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}
The mechanism of the vapor–gas deposition of vinyltrimethoxysilane (VS) and ethylene glycol (EG) from azeotropic solutions is investigated, which allows a reduction of the evaporation temperature of the components of working mixtures. The need for such studies is associated with the development of a new direction in the technology of vapor–gas deposition of polymer coatings. Methods have been developed for monitoring the chemical composition of working solutions in evaporators using optical spectroscopy, which makes it possible to calculate the partial pressures of vapor-phase components. Based on these studies, compositions of working solutions are proposed that allow the equalization of the partial pressures of the components of working mixtures with a large difference in the boiling point. With the aid of vapor–gas deposition, siloxane coatings on low-carbon steel were obtained, the protective properties of which exceeded the treatment with volatile inhibitors of the adsorption type by two to three orders of magnitude. A new method of vapor–gas deposition of non-volatile powder inhibitors on metals is proposed. Chemical compositions of siloxane coatings were determined using XPS, and mechanisms of interaction of VS with the polymerization promoters ethylene glycol and 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) were proposed.
{"title":"Vapor–Gas Deposition of Polymer Coatings on Metals from Azeotropic Solutions of Organosilanes","authors":"Yury B Makarychev","doi":"10.3390/surfaces6030021","DOIUrl":"https://doi.org/10.3390/surfaces6030021","url":null,"abstract":"The mechanism of the vapor–gas deposition of vinyltrimethoxysilane (VS) and ethylene glycol (EG) from azeotropic solutions is investigated, which allows a reduction of the evaporation temperature of the components of working mixtures. The need for such studies is associated with the development of a new direction in the technology of vapor–gas deposition of polymer coatings. Methods have been developed for monitoring the chemical composition of working solutions in evaporators using optical spectroscopy, which makes it possible to calculate the partial pressures of vapor-phase components. Based on these studies, compositions of working solutions are proposed that allow the equalization of the partial pressures of the components of working mixtures with a large difference in the boiling point. With the aid of vapor–gas deposition, siloxane coatings on low-carbon steel were obtained, the protective properties of which exceeded the treatment with volatile inhibitors of the adsorption type by two to three orders of magnitude. A new method of vapor–gas deposition of non-volatile powder inhibitors on metals is proposed. Chemical compositions of siloxane coatings were determined using XPS, and mechanisms of interaction of VS with the polymerization promoters ethylene glycol and 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) were proposed.","PeriodicalId":22129,"journal":{"name":"Surfaces","volume":"127 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76703761","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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