An atmospheric pressure plasma jet (APPJ) is used to process electrochemically deposited NiFe on carbon paper (NiFe/CP). The reactive oxygen and nitrogen species (RONs) of the APPJ modify the surface properties, chemical bonding types, and oxidation states of the material at the self-sustained temperature of the APPJ. The APPJ treatment further enhances the hydrophilicity and creates a higher disorder level in the carbon material. Moreover, the metal carbide bonds of NiFe/CP formed in the electrochemical deposition (ED) process are converted to metal oxide bonds after APPJ processing. The potential application of APPJ treatment on NiFe/CP in alkaline water electrolysis is demonstrated. With more oxygen-containing species and better hydrophilicity after APPJ treatment, APPJ-treated NiFe/CP is applied as the electrocatalyst for the oxygen evolution reaction (OER) in alkaline water electrolysis. APPJ-treated NiFe/CP is also used in a custom-made anion-exchange membrane water electrolyzer (AEMWE); this should contribute toward realizing the practical large-scale application of AEM for hydrogen production.
{"title":"Direct Current Pulse Atmospheric Pressure Plasma Jet Treatment on Electrochemically Deposited NiFe/Carbon Paper and Its Potential Application in an Anion-Exchange Membrane Water Electrolyzer.","authors":"Shuo-En Yu, Yu-Lun Su, I-Chih Ni, Yi-Cheng Chuang, Cheng-Che Hsu, Chih-I Wu, Yong-Song Chen, I-Chun Cheng, Jian-Zhang Chen","doi":"10.1021/acs.langmuir.4c01169","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c01169","url":null,"abstract":"<p><p>An atmospheric pressure plasma jet (APPJ) is used to process electrochemically deposited NiFe on carbon paper (NiFe/CP). The reactive oxygen and nitrogen species (RONs) of the APPJ modify the surface properties, chemical bonding types, and oxidation states of the material at the self-sustained temperature of the APPJ. The APPJ treatment further enhances the hydrophilicity and creates a higher disorder level in the carbon material. Moreover, the metal carbide bonds of NiFe/CP formed in the electrochemical deposition (ED) process are converted to metal oxide bonds after APPJ processing. The potential application of APPJ treatment on NiFe/CP in alkaline water electrolysis is demonstrated. With more oxygen-containing species and better hydrophilicity after APPJ treatment, APPJ-treated NiFe/CP is applied as the electrocatalyst for the oxygen evolution reaction (OER) in alkaline water electrolysis. APPJ-treated NiFe/CP is also used in a custom-made anion-exchange membrane water electrolyzer (AEMWE); this should contribute toward realizing the practical large-scale application of AEM for hydrogen production.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464365","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-29DOI: 10.1021/acs.langmuir.4c01505
Rui Wang, Chengwei Wang, Yanan Liao, Kai Liu, Weian Wang, Fangfang Wang, Lei Wang, Chunxiang Xu, Feng Chen
Methylammonium lead halide perovskites with highly efficient pure-color or white-light generation have gained increasing scientific interest and promote the development of a great commercial opportunity in displays, lighting, and other applications. However, the poor stabilities, lead toxicity, and unfriendly solvents and ligands in the growth process severely restrict their commercial application. Here, we proposed a green method for preparing uniform and stable polymer-encapsulated photoluminescence (PL) tunable CH3NH3PbBr3–xClx NC thin films at room temperature. Utilizing the swelling effect between alcohol compounds and organic polymers and the ionization of NaCl in methanol solution, the anion exchange process can be achieved rapidly within 7 min. Moreover, the PL wavelengths of the CH3NH3PbBr3–xClx NCs films were precisely tuned with steps as fine as 2 nm. Experimental results showed that NaCl dissolved in methanol solution can form Cl–(CH3OH)n, which brings ionized Cl into the polymer-encapsulated CH3NH3PbBr3 NCs film for CH3NH3PbBr3–xClx NCs film growth. Based on the swelling and anion exchange dynamics, a modified NaCl-CH3OH-MABr solution system was developed to trigger CH3NH3PbBr3–xClx NCs film PL emission tuning from 528 to 463 nm with several-fold intensity enhancement. The realization of precisely controlled photoluminescence from the perovskite nanocrystal film would have wide applications in the optical and imaging fields.
{"title":"Precise Control Light Emission of PVDF-CH3NH3PbBr3–xClx Nanocrystalline Films Using a Cl–(CH3OH)n System","authors":"Rui Wang, Chengwei Wang, Yanan Liao, Kai Liu, Weian Wang, Fangfang Wang, Lei Wang, Chunxiang Xu, Feng Chen","doi":"10.1021/acs.langmuir.4c01505","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c01505","url":null,"abstract":"Methylammonium lead halide perovskites with highly efficient pure-color or white-light generation have gained increasing scientific interest and promote the development of a great commercial opportunity in displays, lighting, and other applications. However, the poor stabilities, lead toxicity, and unfriendly solvents and ligands in the growth process severely restrict their commercial application. Here, we proposed a green method for preparing uniform and stable polymer-encapsulated photoluminescence (PL) tunable CH<sub>3</sub>NH<sub>3</sub>PbBr<sub>3–<i>x</i></sub>Cl<sub><i>x</i></sub> NC thin films at room temperature. Utilizing the swelling effect between alcohol compounds and organic polymers and the ionization of NaCl in methanol solution, the anion exchange process can be achieved rapidly within 7 min. Moreover, the PL wavelengths of the CH<sub>3</sub>NH<sub>3</sub>PbBr<sub>3–<i>x</i></sub>Cl<sub><i>x</i></sub> NCs films were precisely tuned with steps as fine as 2 nm. Experimental results showed that NaCl dissolved in methanol solution can form Cl<sup>–</sup>(CH<sub>3</sub>OH)<sub><i>n</i></sub>, which brings ionized Cl into the polymer-encapsulated CH<sub>3</sub>NH<sub>3</sub>PbBr<sub>3</sub> NCs film for CH<sub>3</sub>NH<sub>3</sub>PbBr<sub>3–<i>x</i></sub>Cl<sub><i>x</i></sub> NCs film growth. Based on the swelling and anion exchange dynamics, a modified NaCl-CH<sub>3</sub>OH-MABr solution system was developed to trigger CH<sub>3</sub>NH<sub>3</sub>PbBr<sub>3–<i>x</i></sub>Cl<sub><i>x</i></sub> NCs film PL emission tuning from 528 to 463 nm with several-fold intensity enhancement. The realization of precisely controlled photoluminescence from the perovskite nanocrystal film would have wide applications in the optical and imaging fields.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464026","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-28DOI: 10.1021/acs.langmuir.4c01415
Cong Gao, Yemeng Sun, Zhengjie Miao, Shipeng Chen, Zheng Xi, Qingqing Sun, Jie Han, Rong Guo
Understanding the interaction between metal ions as catalytic centers and supramolecular scaffolds as chiral substrates plays an important role in developing chiral supramolecular catalysts with high enantioselectivity. Herein, we found that compared with l-norleucine chiral amphiphile (l-NorC16), l-methionine chiral amphiphile (l-MetC16) with the only heteroatom of S site difference in the hydrophilic group can form a similar supramolecular chiral nanoribbon (NR) with the bilayer structure through the self-assembly approach; yet, the interaction between the Cu(II) ion catalytic centers and supramolecular scaffolds is reinforced, favoring the chirality transfer and therefore enhancing their catalytic enantioselectivity of Diels-Alder reaction from 23% [l-NorC16-NR-Cu(II)] to 78% [l-MetC16-NR-Cu(II)]. Our work demonstrates a new strategy from the perspective of strengthening the metal ion-supramolecular scaffold interaction for the preparation of chiral supramolecular catalysts with good catalytic enantioselectivity.
{"title":"Chiral Supramolecular Self-Assembly Catalysts with Enhanced Metal Ion Interaction for Higher Enantioselectivity.","authors":"Cong Gao, Yemeng Sun, Zhengjie Miao, Shipeng Chen, Zheng Xi, Qingqing Sun, Jie Han, Rong Guo","doi":"10.1021/acs.langmuir.4c01415","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c01415","url":null,"abstract":"<p><p>Understanding the interaction between metal ions as catalytic centers and supramolecular scaffolds as chiral substrates plays an important role in developing chiral supramolecular catalysts with high enantioselectivity. Herein, we found that compared with l-norleucine chiral amphiphile (l-NorC<sub>16</sub>), l-methionine chiral amphiphile (l-MetC<sub>16</sub>) with the only heteroatom of S site difference in the hydrophilic group can form a similar supramolecular chiral nanoribbon (NR) with the bilayer structure through the self-assembly approach; yet, the interaction between the Cu(II) ion catalytic centers and supramolecular scaffolds is reinforced, favoring the chirality transfer and therefore enhancing their catalytic enantioselectivity of Diels-Alder reaction from 23% [l-NorC<sub>16</sub>-NR-Cu(II)] to 78% [l-MetC<sub>16</sub>-NR-Cu(II)]. Our work demonstrates a new strategy from the perspective of strengthening the metal ion-supramolecular scaffold interaction for the preparation of chiral supramolecular catalysts with good catalytic enantioselectivity.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464364","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-28DOI: 10.1021/acs.langmuir.4c01813
Jiang Yang*, Rongrong Fan, Yingcheng Li, Xiujuan He and Xiaolong Zhao*,
Surfactants are widely used as foaming agents to remove liquid accumulation in gas wells, enhancing natural gas production. The surfactant used in traditional foam sticks was dissolved and released as foam in a short period, especially at elevated downhole temperatures. This often requires the addition of foam sticks to maintain foam. To solve this problem, this study studies the utilization of nano silica to incorporate the amphoteric surfactant, cocamidopropyl betaine (CAB), into the mesoporous structure of silica nanocomposite as foam sticks for controlled release of CAB. Mesoporous nano silica was prepared by a sol–gel acid-catalyzed process with a silica precursor. The formation of nanocomposite solid sticks containing the amphoteric surfactant was achieved by aging and drying. The composite was characterized by various techniques: infrared spectroscopy, thermogravimetric analysis, energy-dispersive spectrometry, scanning electron microscopy, transmission electron microscopy, and small-angle X-ray diffraction. Results showed that 49.3% of CAB was encapsulated within the mesoporous structure of 30–50 nm nano silica. CAB release over time in aqueous solution at 130 °C exhibited 10.1% surfactant left in the nanocomposite after 72 h, as determined by thermal analysis. Surfactant release was systematically evaluated through foam performance tests. The study revealed that CAB could be control-released over 168 h via CAB diffusion from mesoporous silica. This study provides a longer-lasting foam method to enhance gas production by utilizing mesoporous silica as a control release medium for gas well deliquification.
{"title":"Controlled Release of Amphoteric Surfactant from Mesoporous Nanosilica To Enhance Natural Gas Production at High Temperatures","authors":"Jiang Yang*, Rongrong Fan, Yingcheng Li, Xiujuan He and Xiaolong Zhao*, ","doi":"10.1021/acs.langmuir.4c01813","DOIUrl":"10.1021/acs.langmuir.4c01813","url":null,"abstract":"<p >Surfactants are widely used as foaming agents to remove liquid accumulation in gas wells, enhancing natural gas production. The surfactant used in traditional foam sticks was dissolved and released as foam in a short period, especially at elevated downhole temperatures. This often requires the addition of foam sticks to maintain foam. To solve this problem, this study studies the utilization of nano silica to incorporate the amphoteric surfactant, cocamidopropyl betaine (CAB), into the mesoporous structure of silica nanocomposite as foam sticks for controlled release of CAB. Mesoporous nano silica was prepared by a sol–gel acid-catalyzed process with a silica precursor. The formation of nanocomposite solid sticks containing the amphoteric surfactant was achieved by aging and drying. The composite was characterized by various techniques: infrared spectroscopy, thermogravimetric analysis, energy-dispersive spectrometry, scanning electron microscopy, transmission electron microscopy, and small-angle X-ray diffraction. Results showed that 49.3% of CAB was encapsulated within the mesoporous structure of 30–50 nm nano silica. CAB release over time in aqueous solution at 130 °C exhibited 10.1% surfactant left in the nanocomposite after 72 h, as determined by thermal analysis. Surfactant release was systematically evaluated through foam performance tests. The study revealed that CAB could be control-released over 168 h via CAB diffusion from mesoporous silica. This study provides a longer-lasting foam method to enhance gas production by utilizing mesoporous silica as a control release medium for gas well deliquification.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464008","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-28DOI: 10.1021/acs.langmuir.4c00639
Daniel C. Martin, Daniel T. Elg, Hernan E. Delgado, Hoang M. Nguyen, Paul Rumbach, David M. Bartels, David B. Go
It is known that glow discharges with a water anode inject and form solvated electrons at the plasma–liquid interface, driving a wide variety of reduction reactions. However, in systems with a water cathode, the production and role of solvated electrons are less clear. Here, we present evidence for the direct detection of solvated electrons produced at the interface of an argon plasma and a water cathode via absorption spectroscopy. We further quantify their yield using the dissociative electron attachment of chloroacetate, measuring a yield of 1.04 ± 0.59 electrons per incident ion, corresponding to approximately 100% faradaic efficiency. Additionally, we estimate a yield of 2.09 ± 0.93 hydroxyl radicals per incident ion. Comparison of this yield with other findings in the literature supports that these hydroxyl radicals are likely formed directly in the liquid phase rather than by diffusion from the vapor phase.
{"title":"Optical and Chemical Measurements of Solvated Electrons Produced in Plasma Electrolysis with a Water Cathode","authors":"Daniel C. Martin, Daniel T. Elg, Hernan E. Delgado, Hoang M. Nguyen, Paul Rumbach, David M. Bartels, David B. Go","doi":"10.1021/acs.langmuir.4c00639","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c00639","url":null,"abstract":"It is known that glow discharges with a water anode inject and form solvated electrons at the plasma–liquid interface, driving a wide variety of reduction reactions. However, in systems with a water cathode, the production and role of solvated electrons are less clear. Here, we present evidence for the direct detection of solvated electrons produced at the interface of an argon plasma and a water cathode via absorption spectroscopy. We further quantify their yield using the dissociative electron attachment of chloroacetate, measuring a yield of 1.04 ± 0.59 electrons per incident ion, corresponding to approximately 100% faradaic efficiency. Additionally, we estimate a yield of 2.09 ± 0.93 hydroxyl radicals per incident ion. Comparison of this yield with other findings in the literature supports that these hydroxyl radicals are likely formed directly in the liquid phase rather than by diffusion from the vapor phase.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464064","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-28DOI: 10.1021/acs.langmuir.4c00664
Ravi Nigam, Kamal K Kar
Supercapacitors store energy due to the formation of an electric double layer (EDL) at the interface of the electrodes and electrolyte. The present article deals with the finite element study of equilibrium electric double layer capacitance (EDLC) in the mixed morphology electrodes comprising all three fundamental crystal structures, simple cubic (SC), body-centered cubic (BCC), and face-centered cubic morphologies (FCC). Mesoporous-activated carbon forms the electrode in the supercapacitor with (C2H5)4NBF4/propylene carbonate organic electrolyte. Electrochemical interference is clearly demonstrated in the supercapacitors with the formation of the potential bands, as in the case of interference theory due to the increasing packing factor. The effects of electrode thickness varying from a wide range of 50 nm to 0.04 mm on specific EDLC have been discussed in detail. The interfacial geometry of the unit cell in contact with the electrolyte is the most important parameter determining the properties of the EDL. The critical thickness of the electrodes is 1.71 μm in all the morphologies. Polarization increases the interfacial potential and leads to EDL formation. The Stern layer specific capacitance is 167.6 μF cm-2 in all the morphologies. The maximum capacitance is in the decreasing order of interfacial geometry, as FCC > BCC > SC, dependent on the packing factor. The minimum transmittance in all the morphologies is 98.35%, with the constant figure of merit at higher electrode thickness having applications in the chip interconnects. The transient analysis shows that the interfacial current decreases with increasing polarization in the EDL. The capacitance also decreases with the increase of the scan rate.
{"title":"Effect of Mixed Morphology (Simple Cubic, Face-Centered Cubic, and Body-Centered Cubic)-Based Electrodes on the Electric Double Layer Capacitance of Supercapacitors.","authors":"Ravi Nigam, Kamal K Kar","doi":"10.1021/acs.langmuir.4c00664","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c00664","url":null,"abstract":"<p><p>Supercapacitors store energy due to the formation of an electric double layer (EDL) at the interface of the electrodes and electrolyte. The present article deals with the finite element study of equilibrium electric double layer capacitance (EDLC) in the mixed morphology electrodes comprising all three fundamental crystal structures, simple cubic (SC), body-centered cubic (BCC), and face-centered cubic morphologies (FCC). Mesoporous-activated carbon forms the electrode in the supercapacitor with (C<sub>2</sub>H<sub>5</sub>)<sub>4</sub>NBF<sub>4</sub>/propylene carbonate organic electrolyte. Electrochemical interference is clearly demonstrated in the supercapacitors with the formation of the potential bands, as in the case of interference theory due to the increasing packing factor. The effects of electrode thickness varying from a wide range of 50 nm to 0.04 mm on specific EDLC have been discussed in detail. The interfacial geometry of the unit cell in contact with the electrolyte is the most important parameter determining the properties of the EDL. The critical thickness of the electrodes is 1.71 μm in all the morphologies. Polarization increases the interfacial potential and leads to EDL formation. The Stern layer specific capacitance is 167.6 μF cm<sup>-2</sup> in all the morphologies. The maximum capacitance is in the decreasing order of interfacial geometry, as FCC > BCC > SC, dependent on the packing factor. The minimum transmittance in all the morphologies is 98.35%, with the constant figure of merit at higher electrode thickness having applications in the chip interconnects. The transient analysis shows that the interfacial current decreases with increasing polarization in the EDL. The capacitance also decreases with the increase of the scan rate.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464366","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Metal oxides can activate peroxymonosulfate (PMS) for the catalytic degradation of organic dyes. However, achieving high catalytic efficiency, structural stability, ease of recovery, and recyclability remains challenging for both research and practical applications. To address these requirements, a bimetallic oxide, CuMnO2, was synthesized using a simple hydrothermal approach and was encapsulated to create hydrogel beads, CS-Ca@PEI/CuMnO2. Subsequently, CS-Ca@PEI/CuMnO2 was used to activate PMS and establish a solid–liquid heterogeneous oxidation system (CS-Ca@PEI/CuMnO2/PMS) for the degradation of Congo red (CR). The effects of various parameters such as different systems, catalyst dosages, initial pH values, PMS concentrations, temperatures, and anion types on the catalytic degradation properties of CS-Ca@PEI/CuMnO2 for CR were systematically evaluated. The results indicated that CS-Ca@PEI/CuMnO2 has exceptional degradation capacity, achieving 91.0% degradation of CR at pH 7. After three degradation cycles, the catalyst maintained an 86.9% degradation efficiency compared to its original performance, highlighting its robust structural stability. The presence of reactive radicals, specifically 1O2 and •O2–, were confirmed through quenching experiments, X-ray photoelectron spectroscopy (XPS), and electron paramagnetic resonance spectroscopy (EPR). Liquid chromatography-tandem mass spectrometry (LC-MS) revealed ten proposed intermediates in the catalytic degradation process. Due to its exceptional catalytic performance, structural durability, recyclability, and ease of retrieval, the catalyst shows great potential for effectively removing organic pollutants from industrial wastewater.
{"title":"Reusable CS-Ca@PEI/CuMnO2 Hydrogel Beads for Peroxymonosulfate-Activated Degradation of Congo Red","authors":"Jinyan Yang, Zhaoxing Hu, Wenhui Rao, Yijun Xie, Chuanbai Yu","doi":"10.1021/acs.langmuir.4c00659","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c00659","url":null,"abstract":"Metal oxides can activate peroxymonosulfate (PMS) for the catalytic degradation of organic dyes. However, achieving high catalytic efficiency, structural stability, ease of recovery, and recyclability remains challenging for both research and practical applications. To address these requirements, a bimetallic oxide, CuMnO<sub>2</sub>, was synthesized using a simple hydrothermal approach and was encapsulated to create hydrogel beads, CS-Ca@PEI/CuMnO<sub>2</sub>. Subsequently, CS-Ca@PEI/CuMnO<sub>2</sub> was used to activate PMS and establish a solid–liquid heterogeneous oxidation system (CS-Ca@PEI/CuMnO<sub>2</sub>/PMS) for the degradation of Congo red (CR). The effects of various parameters such as different systems, catalyst dosages, initial pH values, PMS concentrations, temperatures, and anion types on the catalytic degradation properties of CS-Ca@PEI/CuMnO<sub>2</sub> for CR were systematically evaluated. The results indicated that CS-Ca@PEI/CuMnO<sub>2</sub> has exceptional degradation capacity, achieving 91.0% degradation of CR at pH 7. After three degradation cycles, the catalyst maintained an 86.9% degradation efficiency compared to its original performance, highlighting its robust structural stability. The presence of reactive radicals, specifically <sup>1</sup>O<sub>2</sub> and <sup>•</sup>O<sub>2</sub><sup>–</sup>, were confirmed through quenching experiments, X-ray photoelectron spectroscopy (XPS), and electron paramagnetic resonance spectroscopy (EPR). Liquid chromatography-tandem mass spectrometry (LC-MS) revealed ten proposed intermediates in the catalytic degradation process. Due to its exceptional catalytic performance, structural durability, recyclability, and ease of retrieval, the catalyst shows great potential for effectively removing organic pollutants from industrial wastewater.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464004","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-27DOI: 10.1021/acs.langmuir.4c01163
Hassanin M. Ali, Farzaneh Arabpour Roghabadi*, Vahid Ahmadi, Ahdieh Amjadi and Iraj Ghaedi,
In this work, a heterogeneous photocatalysis system is fabricated for treating wastewater containing organic dyes and pharmaceutical substances. Double-heterojunction Janus photocatalysts are formed on the surface of size-tunable polydimethylsiloxane (PDMS) microparticles shaped via simple and low-cost coflow microfluidic devices. Ag0/Ag0-TiO2/TiO2 Janus-like photocatalysts are synthesized on the surface of porous PDMS microparticles as the support in which the metal–semiconductor heterojunction of Ag0/Ag0-TiO2 and the second heterojunction of Ag0-TiO2/TiO2 are created in situ, leading to the formation of Ag0/Ag0-TiO2/TiO2@PDMS photocatalysis systems. To form the heterojunctions on the PDMS surface, the polymer chain etching method is employed as a desired strategy to have half of the TiO2 nanoparticles on the surface of microparticles, which are treated by a Ag source. Using salt additives and the etching method, PDMS microparticles are made porous, providing more surface area for photoreactions. Surprisingly, the highest decomposition efficiencies of 94.4 and 91.1% are achieved for rhodamine B(RhB) and tetracycline (TC), respectively, under visible light for 60 min pH 11, a light source at a distance of 2 cm, 5 mM AgNO3, 10 wt % TiO2, 7 wt % NaCl, and 20 gm/L photocatalyst, which are conditions that result in the best performance for RhB degradation. Regarding the stability of the photocatalysts, no significant change is observed in the performance after five cycles.
{"title":"Wastewater Treatment Using High-Performance In Situ Formed Double-Heterojunction Janus Photocatalyst Microparticles Shaped via a Microfluidic Device","authors":"Hassanin M. Ali, Farzaneh Arabpour Roghabadi*, Vahid Ahmadi, Ahdieh Amjadi and Iraj Ghaedi, ","doi":"10.1021/acs.langmuir.4c01163","DOIUrl":"10.1021/acs.langmuir.4c01163","url":null,"abstract":"<p >In this work, a heterogeneous photocatalysis system is fabricated for treating wastewater containing organic dyes and pharmaceutical substances. Double-heterojunction Janus photocatalysts are formed on the surface of size-tunable polydimethylsiloxane (PDMS) microparticles shaped via simple and low-cost coflow microfluidic devices. Ag<sup>0</sup>/Ag<sup>0</sup>-TiO<sub>2</sub>/TiO<sub>2</sub> Janus-like photocatalysts are synthesized on the surface of porous PDMS microparticles as the support in which the metal–semiconductor heterojunction of Ag<sup>0</sup>/Ag<sup>0</sup>-TiO<sub>2</sub> and the second heterojunction of Ag<sup>0</sup>-TiO<sub>2</sub>/TiO<sub>2</sub> are created in situ, leading to the formation of Ag<sup>0</sup>/Ag<sup>0</sup>-TiO<sub>2</sub>/TiO<sub>2</sub>@PDMS photocatalysis systems. To form the heterojunctions on the PDMS surface, the polymer chain etching method is employed as a desired strategy to have half of the TiO<sub>2</sub> nanoparticles on the surface of microparticles, which are treated by a Ag source. Using salt additives and the etching method, PDMS microparticles are made porous, providing more surface area for photoreactions. Surprisingly, the highest decomposition efficiencies of 94.4 and 91.1% are achieved for rhodamine B(RhB) and tetracycline (TC), respectively, under visible light for 60 min pH 11, a light source at a distance of 2 cm, 5 mM AgNO<sub>3</sub>, 10 wt % TiO<sub>2</sub>, 7 wt % NaCl, and 20 gm/L photocatalyst, which are conditions that result in the best performance for RhB degradation. Regarding the stability of the photocatalysts, no significant change is observed in the performance after five cycles.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464047","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-27DOI: 10.1021/acs.langmuir.4c01561
Georgios Karchilakis, Spyridon Varlas, Edwin C. Johnson*, Oleta Norvilaite, Matthew A. H. Farmer, George Sanderson, Graham J. Leggett and Steven P. Armes*,
Compared to lipids, block copolymer vesicles are potentially robust nanocontainers for enzymes owing to their enhanced chemical stability, particularly in challenging environments. Herein we report that cis-diol-functional diblock copolymer vesicles can be chemically adsorbed onto a hydrophilic aldehyde-functional polymer brush via acetal bond formation under mild conditions (pH 5.5, 20 °C). Quartz crystal microbalance studies indicated an adsorbed amount, Γ, of 158 mg m–2 for vesicle adsorption onto such brushes, whereas negligible adsorption (Γ = 0.1 mg m–2) was observed for a control experiment conducted using a cis-diol-functionalized brush. Scanning electron microscopy and ellipsometry studies indicated a mean surface coverage of around 30% at the brush surface, which suggests reasonably efficient chemical adsorption. Importantly, such vesicles can be conveniently loaded with a model enzyme (horseradish peroxidase, HRP) using an aqueous polymerization-induced self-assembly formulation. Moreover, the immobilized vesicles remained permeable toward small molecules while retaining their enzyme payload. The enzymatic activity of such HRP-loaded vesicles was demonstrated using a well-established colorimetric assay. In principle, this efficient vesicle-on-brush strategy can be applied to a wide range of enzymes and functional proteins for the design of next-generation immobilized nanoreactors for enzyme-mediated catalysis.
{"title":"Capturing Enzyme-Loaded Diblock Copolymer Vesicles Using an Aldehyde-Functionalized Hydrophilic Polymer Brush","authors":"Georgios Karchilakis, Spyridon Varlas, Edwin C. Johnson*, Oleta Norvilaite, Matthew A. H. Farmer, George Sanderson, Graham J. Leggett and Steven P. Armes*, ","doi":"10.1021/acs.langmuir.4c01561","DOIUrl":"10.1021/acs.langmuir.4c01561","url":null,"abstract":"<p >Compared to lipids, block copolymer vesicles are potentially robust nanocontainers for enzymes owing to their enhanced chemical stability, particularly in challenging environments. Herein we report that <i>cis</i>-diol-functional diblock copolymer vesicles can be chemically adsorbed onto a hydrophilic aldehyde-functional polymer brush via acetal bond formation under mild conditions (pH 5.5, 20 °C). Quartz crystal microbalance studies indicated an adsorbed amount, Γ, of 158 mg m<sup>–2</sup> for vesicle adsorption onto such brushes, whereas negligible adsorption (Γ = 0.1 mg m<sup>–2</sup>) was observed for a control experiment conducted using a <i>cis</i>-diol-functionalized brush. Scanning electron microscopy and ellipsometry studies indicated a mean surface coverage of around 30% at the brush surface, which suggests reasonably efficient chemical adsorption. Importantly, such vesicles can be conveniently loaded with a model enzyme (horseradish peroxidase, HRP) using an aqueous polymerization-induced self-assembly formulation. Moreover, the immobilized vesicles remained permeable toward small molecules while retaining their enzyme payload. The enzymatic activity of such HRP-loaded vesicles was demonstrated using a well-established colorimetric assay. In principle, this efficient vesicle-on-brush strategy can be applied to a wide range of enzymes and functional proteins for the design of next-generation immobilized nanoreactors for enzyme-mediated catalysis.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.langmuir.4c01561","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141453717","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-27DOI: 10.1021/acs.langmuir.4c01633
Haidong Jia, Han Jia*, Qiuxia Wang, Yingbiao Xu, Bowen Wang, Qiang Wang, Xu Li, Zhe Wang, Kaihe Lv and Pan Huang,
A novel polymeric ionic liquid (PDBA-IL-NH2) using imidazolium ionic liquids with short alkyl chains as monomers and two control ionic liquids (PDBA-IL-OH and PIL-NH2) were synthesized. Their inhibition properties and mechanisms were explored via surface analysis, weight loss tests, electrochemical studies, and adsorption isotherm analysis. The corrosion inhibition efficiency (CIE) of PDBA-IL-NH2 gradually increased with increasing concentration, and the largest efficiency was 94.67% at 100 ppm. At the same concentration (50 ppm), the corrosion inhibition abilities of inhibitors were in the order of PDBA-IL-NH2 > PDBA-IL-OH > PIL-NH2 > IL-NH2. Based on the experimental investigation, the synergistic effect of electrostatic interaction, protonation, and electron donor–acceptor interaction facilitated the intensive entanglement and coverage of PDBA-IL-NH2 with the reticulated form on the metal, and the generated densest films protected the metal from the corrosive media. Ultimately, the theoretical results of molecular dynamics simulations and quantum chemical study were in high agreement with the experimental data, which confirmed the proposed inhibition mechanisms on the microscopic scale. This study contributed valuable perspectives to the design of efficient and ecofriendly corrosion inhibitors.
{"title":"Imidazolium-Based Polymeric Ionic Liquids with Short Alkyl Chains as Green Corrosion Inhibitors for Mild Steel in 1 M HCl: Experimental and Theoretical Investigations","authors":"Haidong Jia, Han Jia*, Qiuxia Wang, Yingbiao Xu, Bowen Wang, Qiang Wang, Xu Li, Zhe Wang, Kaihe Lv and Pan Huang, ","doi":"10.1021/acs.langmuir.4c01633","DOIUrl":"10.1021/acs.langmuir.4c01633","url":null,"abstract":"<p >A novel polymeric ionic liquid (PDBA-IL-NH<sub>2</sub>) using imidazolium ionic liquids with short alkyl chains as monomers and two control ionic liquids (PDBA-IL-OH and PIL-NH<sub>2</sub>) were synthesized. Their inhibition properties and mechanisms were explored via surface analysis, weight loss tests, electrochemical studies, and adsorption isotherm analysis. The corrosion inhibition efficiency (CIE) of PDBA-IL-NH<sub>2</sub> gradually increased with increasing concentration, and the largest efficiency was 94.67% at 100 ppm. At the same concentration (50 ppm), the corrosion inhibition abilities of inhibitors were in the order of PDBA-IL-NH<sub>2</sub> > PDBA-IL-OH > PIL-NH<sub>2</sub> > IL-NH<sub>2</sub>. Based on the experimental investigation, the synergistic effect of electrostatic interaction, protonation, and electron donor–acceptor interaction facilitated the intensive entanglement and coverage of PDBA-IL-NH<sub>2</sub> with the reticulated form on the metal, and the generated densest films protected the metal from the corrosive media. Ultimately, the theoretical results of molecular dynamics simulations and quantum chemical study were in high agreement with the experimental data, which confirmed the proposed inhibition mechanisms on the microscopic scale. This study contributed valuable perspectives to the design of efficient and ecofriendly corrosion inhibitors.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141453738","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}