The synthesis of ammonia (NH3) via the Haber–Bosch process is energy-intensive and environmentally challenging, necessitating the development of sustainable alternatives. Herein, we report a directed etch template strategy to create atomically dispersed Ru–N4 active sites within layered porous carbon (NC@Ru) for efficient electrochemical nitrogen reduction reaction (NRR). The removal of the MgO template results in an interconnected carbon network with hierarchical porous structures, significantly enhancing the accessibility and mass transfer of the active sites. The NC@Ru catalyst demonstrated superior NRR performance, achieving an ammonia yield rate of 196.2 μg h–1 mgcat.–1 and a Faradaic efficiency of 43.8%. In situ electrochemical mass spectrometry was employed to analyze NRR kinetics, while density functional theory calculations were utilized to elucidate the NRR mechanism and identify the rate-determining step. The work introduces a novel high-performance catalyst for electrocatalytic NRR and provides a practical strategy for optimizing active-site microenvironments, laying the groundwork for future commercial applications of electrocatalytic NRR.
{"title":"Modulation of Atomically Dispersed Ru Microenvironments by a Directed Etch Template Strategy for Efficient Nitrogen Fixation","authors":"Zhiya Han, Jiaxi Yuan, Gaijuan Guo, Yue Kang, Yixin Liu, Chunxia Zhou, Liping Tong, Binfeng Lu, Xiyang Liu, Quan Wang, Miaosen Yang, Senhe Huang, Boxu Feng, Sheng Han","doi":"10.1021/acsanm.4c02608","DOIUrl":"https://doi.org/10.1021/acsanm.4c02608","url":null,"abstract":"The synthesis of ammonia (NH<sub>3</sub>) via the Haber–Bosch process is energy-intensive and environmentally challenging, necessitating the development of sustainable alternatives. Herein, we report a directed etch template strategy to create atomically dispersed Ru–N<sub>4</sub> active sites within layered porous carbon (NC@Ru) for efficient electrochemical nitrogen reduction reaction (NRR). The removal of the MgO template results in an interconnected carbon network with hierarchical porous structures, significantly enhancing the accessibility and mass transfer of the active sites. The NC@Ru catalyst demonstrated superior NRR performance, achieving an ammonia yield rate of 196.2 μg h<sup>–1</sup> mg<sub>cat.</sub><sup>–1</sup> and a Faradaic efficiency of 43.8%. In situ electrochemical mass spectrometry was employed to analyze NRR kinetics, while density functional theory calculations were utilized to elucidate the NRR mechanism and identify the rate-determining step. The work introduces a novel high-performance catalyst for electrocatalytic NRR and provides a practical strategy for optimizing active-site microenvironments, laying the groundwork for future commercial applications of electrocatalytic NRR.","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":null,"pages":null},"PeriodicalIF":5.9,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141525263","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}
Jiawei Zhang, Tiantian Guo, Kunlun Liu, Ke Bao, Xinyi Liu, Sifan Cui, Dixuan Chen, Mulin Jun Li, Siqi Bao, Chunhong Hu, Xi Wei, Xiujun Gao
In recent years, the application of hollow mesoporous silicon nanoparticles in the biomedical field has attracted much attention because of their excellent features. In this study, the sonosensitizer curcumin (Cur), the chemotherapy drug doxorubicin (Dox), and the perfluoropropane (C3F8) gas were loaded into a multifunctional hollow mesoporous silica nanoparticle (MHMSN). The surface of MHMSN was modified with a biotin molecule and acid-sensitive groups (cis-aconitic anhydride-polyethylene glycol, CDM-PEG). The as-prepared multifunctional nanoparticle (CDF-MHMSN) demonstrates improved therapeutic efficacy and enhanced tumor contrast ultrasound performance. Surface-modified CDM-PEG can improve the blood circulation ability of nanoparticles and peel off in the acidic tumor microenvironment, which can enhance the endocytosis of cancer cells. As a sonosensitizer, Cur could generate reactive oxygen species (ROS) under ultrasound stimulation to kill tumor cells and reduce the multidrug resistance of tumor cells to the Dox by inhibiting the expression of P-glycoprotein. Overall, CDF-MHMSN exhibits good biocompatibility, excellent ultrasound imaging capability, and effective antitumor ability, which may contribute to improving the treatment strategy for hepatocellular carcinoma.
近年来，中空介孔硅纳米颗粒因其优异的特性在生物医学领域的应用备受关注。本研究将声敏剂姜黄素（Cur）、化疗药物多柔比星（Dox）和全氟丙烷（C3F8）气体载入多功能中空介孔硅纳米颗粒（MHMSN）。MHMSN 表面修饰了生物素分子和酸敏感基团（顺式乌头酸酐-聚乙二醇，CDM-PEG）。制备的多功能纳米粒子（CDF-MHMSN）具有更好的疗效和更强的肿瘤对比超声性能。表面修饰的 CDM-PEG 可提高纳米粒子的血液循环能力，并在酸性肿瘤微环境中剥离，从而增强对癌细胞的内吞作用。作为一种声敏剂，Cur 能在超声刺激下产生活性氧（ROS），杀死肿瘤细胞，并通过抑制 P 糖蛋白的表达，降低肿瘤细胞对 Dox 的多药耐药性。总之，CDF-MHMSN具有良好的生物相容性、优异的超声成像能力和有效的抗肿瘤能力，有助于改善肝细胞癌的治疗策略。
{"title":"Ultrasonic Diagnosis and Treatment of Tumors Using Multifunctional Hollow Mesoporous Silicon Nanoparticles","authors":"Jiawei Zhang, Tiantian Guo, Kunlun Liu, Ke Bao, Xinyi Liu, Sifan Cui, Dixuan Chen, Mulin Jun Li, Siqi Bao, Chunhong Hu, Xi Wei, Xiujun Gao","doi":"10.1021/acsanm.4c02319","DOIUrl":"https://doi.org/10.1021/acsanm.4c02319","url":null,"abstract":"In recent years, the application of hollow mesoporous silicon nanoparticles in the biomedical field has attracted much attention because of their excellent features. In this study, the sonosensitizer curcumin (Cur), the chemotherapy drug doxorubicin (Dox), and the perfluoropropane (C<sub>3</sub>F<sub>8</sub>) gas were loaded into a multifunctional hollow mesoporous silica nanoparticle (MHMSN). The surface of MHMSN was modified with a biotin molecule and acid-sensitive groups (cis-aconitic anhydride-polyethylene glycol, CDM-PEG). The as-prepared multifunctional nanoparticle (CDF-MHMSN) demonstrates improved therapeutic efficacy and enhanced tumor contrast ultrasound performance. Surface-modified CDM-PEG can improve the blood circulation ability of nanoparticles and peel off in the acidic tumor microenvironment, which can enhance the endocytosis of cancer cells. As a sonosensitizer, Cur could generate reactive oxygen species (ROS) under ultrasound stimulation to kill tumor cells and reduce the multidrug resistance of tumor cells to the Dox by inhibiting the expression of P-glycoprotein. Overall, CDF-MHMSN exhibits good biocompatibility, excellent ultrasound imaging capability, and effective antitumor ability, which may contribute to improving the treatment strategy for hepatocellular carcinoma.","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":null,"pages":null},"PeriodicalIF":5.9,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141525246","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}
Clyde Overby, Baixue Xiao, Tiana Salomon, Jorge Jimenez, Nathaniel Silvia, Danielle S. W. Benoit
Nanoparticle drug-delivery systems (NP DDS) have proven to be tremendously impactful for delivering therapeutic agents in cancer treatments, vaccinations, gene therapy, and diagnostics, and enabled agents such as RNA therapeutics. However, the exposure of NP DDS to biological milieus leads to the rapid adsorption of proteins and other molecules, forming a proteinaceous corona that obscures NP surface characteristics and controls the biological interactions of the NP DDS. Surface modifications, including poly(ethylene glycol) (PEG) and synthetic zwitterionic polymers, reduce protein adsorption yet lack monomer-scale tunability, have off-target immunological effects, and suffer from targeting-limited steric hindrance, altogether motivating the development of alternative approaches. Peptides can uniquely form many zwitterions and have shown promise in reducing and controlling the NP protein corona as a function of the peptide sequence. However, the impact of zwitterionic peptides (ZIPs) on the drug-delivery properties of polymeric NPs has not been explored. In this work, diverse ZIPs computationally predicted to reduce protein adsorption by assessing peptide–peptide β-strand interaction energies were conjugated to pH-responsive cationic NPs. The resulting ZIP-NP conjugates exhibited up to 88% reduced protein adsorption and a range of siRNA-mediated gene knockdown that correlates with interaction energies. These data suggest that the peptide–peptide interaction energy is a promising design parameter for ZIPs for further model development. ZIP-NP also exhibited sequence-dependent variations in cellular uptake and circulation half-life, indicating that ZIP-NPs are suitable for tuning and improving NP drug-delivery characteristics.
{"title":"Rationally Designed Zwitterionic Peptides Improve siRNA Delivery of Cationic Diblock Copolymer-Based Nanoparticle Drug-Delivery Systems","authors":"Clyde Overby, Baixue Xiao, Tiana Salomon, Jorge Jimenez, Nathaniel Silvia, Danielle S. W. Benoit","doi":"10.1021/acsanm.4c01995","DOIUrl":"https://doi.org/10.1021/acsanm.4c01995","url":null,"abstract":"Nanoparticle drug-delivery systems (NP DDS) have proven to be tremendously impactful for delivering therapeutic agents in cancer treatments, vaccinations, gene therapy, and diagnostics, and enabled agents such as RNA therapeutics. However, the exposure of NP DDS to biological milieus leads to the rapid adsorption of proteins and other molecules, forming a proteinaceous corona that obscures NP surface characteristics and controls the biological interactions of the NP DDS. Surface modifications, including poly(ethylene glycol) (PEG) and synthetic zwitterionic polymers, reduce protein adsorption yet lack monomer-scale tunability, have off-target immunological effects, and suffer from targeting-limited steric hindrance, altogether motivating the development of alternative approaches. Peptides can uniquely form many zwitterions and have shown promise in reducing and controlling the NP protein corona as a function of the peptide sequence. However, the impact of zwitterionic peptides (ZIPs) on the drug-delivery properties of polymeric NPs has not been explored. In this work, diverse ZIPs computationally predicted to reduce protein adsorption by assessing peptide–peptide β-strand interaction energies were conjugated to pH-responsive cationic NPs. The resulting ZIP-NP conjugates exhibited up to 88% reduced protein adsorption and a range of siRNA-mediated gene knockdown that correlates with interaction energies. These data suggest that the peptide–peptide interaction energy is a promising design parameter for ZIPs for further model development. ZIP-NP also exhibited sequence-dependent variations in cellular uptake and circulation half-life, indicating that ZIP-NPs are suitable for tuning and improving NP drug-delivery characteristics.","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":null,"pages":null},"PeriodicalIF":5.9,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141525267","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}
Ammonia is recognized as the best carrier for hydrogen storage and transportation. Nanomaterial catalysts have eminent catalytic activity for ammonia decomposition. However, the preparation of low-loading, high-activity noble metal atomically dispersed nanometer ammonia decomposition catalysts and their reaction mechanisms remain obscure. In this work, we report the synthesis of a stable ruthenium (Ru) atomically dispersed catalyst with oxygen-rich defects achieved through hydrogen etching of the support CeO2NR nanorods. The oxygen defects result in the catalyst exhibiting a favorable low-temperature catalytic activity and an exceedingly high atom utilization rate for ammonia decomposition. The hydrogen production rate from ammonia decomposition per unit mass of Ru is as high as 2446 mmol H2 gRu–1 min–1 at 1 bar, 450 °C, and gas hour space velocity = 12,000 mL gcat–1 h–1. In this case, the highly dispersed Ru provided enough active sites, while the oxygen defects of the catalyst enhanced the electron transfer tunnel between Ru and the nanorod support under a Schottky contact model. The detailed mechanism of oxygen defects for improving the catalytic performance of ammonia decomposition was studied by DFT modeling. Thus, this work provides a promising strategy to improve the catalytic efficiency of an atomically dispersed Ru nanocatalyst.
{"title":"Ru Dispersed on Oxygen-Defect-Rich CeO2 Nanorods for Ammonia Decomposition","authors":"Baoshan Teng, Chunhui Ma, Jiayu Chen, Yunlai Zhang, Baohuan Wei, Maohai Sang, Hui Wang, Yuhan Sun","doi":"10.1021/acsanm.4c01416","DOIUrl":"https://doi.org/10.1021/acsanm.4c01416","url":null,"abstract":"Ammonia is recognized as the best carrier for hydrogen storage and transportation. Nanomaterial catalysts have eminent catalytic activity for ammonia decomposition. However, the preparation of low-loading, high-activity noble metal atomically dispersed nanometer ammonia decomposition catalysts and their reaction mechanisms remain obscure. In this work, we report the synthesis of a stable ruthenium (Ru) atomically dispersed catalyst with oxygen-rich defects achieved through hydrogen etching of the support CeO<sub>2</sub>NR nanorods. The oxygen defects result in the catalyst exhibiting a favorable low-temperature catalytic activity and an exceedingly high atom utilization rate for ammonia decomposition. The hydrogen production rate from ammonia decomposition per unit mass of Ru is as high as 2446 mmol H<sub>2</sub> g<sub>Ru</sub><sup>–1</sup> min<sup>–1</sup> at 1 bar, 450 °C, and gas hour space velocity = 12,000 mL g<sub>cat</sub><sup>–1</sup> h<sup>–1</sup>. In this case, the highly dispersed Ru provided enough active sites, while the oxygen defects of the catalyst enhanced the electron transfer tunnel between Ru and the nanorod support under a Schottky contact model. The detailed mechanism of oxygen defects for improving the catalytic performance of ammonia decomposition was studied by DFT modeling. Thus, this work provides a promising strategy to improve the catalytic efficiency of an atomically dispersed Ru nanocatalyst.","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":null,"pages":null},"PeriodicalIF":5.9,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141525342","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}
Haijun Shen, Yane Ma, Chun Zhang, Yi Qiao, Jialing Chen, Feng Sun
The presence of hypoxics, bacterial infection, and the creation of bacterial biofilms are significant obstacles that hinder the healing of diabetic wounds. Calcium peroxide (CaO2) can be hydrolyzed to produce oxygen (O2) and hydrogen peroxide (H2O2), resulting in the simultaneous creation of oxygen and an antimicrobial effect. However, oxygen delivery is limited by the skin and bacterial biofilm barrier. Herein, we proposed a microneedles patch loading CaO2 nanoparticles (abbreviated as CaO2 NPs@MN). The microneedles can puncture the skin and destroy the biofilm barrier. Meanwhile, upon contact with the biological fluid, the microneedles would be dissolved, and CaO2 NPs would be released into the wound site, further being hydrolyzed to O2 and H2O2 to achieve antibacterial effect and local deep oxygen delivery. Notably, in order to encapsulate CaO2 powders evenly into the microneedle tips and avoid their hydrolysis during the preparation process, we fabricated the nanoscaled CaO2 particles and encapsulated them in microneedles in an ethanol system for the first time. The in vitro experiments demonstrated that CaO2 NPs@MN possessed the desired oxygen delivery and antibacterial effect. Furthermore, the elimination of bacteria, reduction in inflammation, promotion of collagen formation, stimulation of blood vessel growth, and subsequent acceleration of wound healing were observed in in vivo experiments. In conclusion, we provided a simple process for the application of CaO2 in wound healing and also a promising strategy for infected diabetic ulcer treatment.
{"title":"Microneedle Patch Loaded with Calcium Peroxide Nanoparticles for Oxygen Healing and Biofilm Inhibition in Diabetic Wound Healing","authors":"Haijun Shen, Yane Ma, Chun Zhang, Yi Qiao, Jialing Chen, Feng Sun","doi":"10.1021/acsanm.4c01973","DOIUrl":"https://doi.org/10.1021/acsanm.4c01973","url":null,"abstract":"The presence of hypoxics, bacterial infection, and the creation of bacterial biofilms are significant obstacles that hinder the healing of diabetic wounds. Calcium peroxide (CaO<sub>2</sub>) can be hydrolyzed to produce oxygen (O<sub>2</sub>) and hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>), resulting in the simultaneous creation of oxygen and an antimicrobial effect. However, oxygen delivery is limited by the skin and bacterial biofilm barrier. Herein, we proposed a microneedles patch loading CaO<sub>2</sub> nanoparticles (abbreviated as CaO<sub>2</sub> NPs@MN). The microneedles can puncture the skin and destroy the biofilm barrier. Meanwhile, upon contact with the biological fluid, the microneedles would be dissolved, and CaO<sub>2</sub> NPs would be released into the wound site, further being hydrolyzed to O<sub>2</sub> and H<sub>2</sub>O<sub>2</sub> to achieve antibacterial effect and local deep oxygen delivery. Notably, in order to encapsulate CaO<sub>2</sub> powders evenly into the microneedle tips and avoid their hydrolysis during the preparation process, we fabricated the nanoscaled CaO<sub>2</sub> particles and encapsulated them in microneedles in an ethanol system for the first time. The <i>in vitro</i> experiments demonstrated that CaO<sub>2</sub> NPs@MN possessed the desired oxygen delivery and antibacterial effect. Furthermore, the elimination of bacteria, reduction in inflammation, promotion of collagen formation, stimulation of blood vessel growth, and subsequent acceleration of wound healing were observed in <i>in vivo</i> experiments. In conclusion, we provided a simple process for the application of CaO<sub>2</sub> in wound healing and also a promising strategy for infected diabetic ulcer treatment.","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":null,"pages":null},"PeriodicalIF":5.9,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141525259","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}
Zhanpeng Luo, Wenhua Wang, Shumei Gao, Guohua Zhao, Xiaoqiang Wang
In this study, Nb modification was applied to promote the performance of selective catalytic reduction (SCR) of NOx and NH4HSO4 (ABS) resistance of pure silica molecular sieve KIT-6-supported copper nanoporous catalysts. Experimental results revealed that the optimal Cu5–NK sample possessed above 80% deNOx efficiency with good N2 selectivity in the temperature range of 260–400 °C and ABS deposition only reduced the SCR efficiency of the Cu5–NK sample by 20% at 320 °C. Characterization results indicated that Nb modification would induce formation of strong interactions with Cu, which enlarged pore size, amplified dispersion of active Cu species, and enhanced redox ability and surface acidity. Importantly, the enlarged pore size could weaken the thermal stability of ABS and promote its decomposition, while more active Cu sites retained by strong Cu–Nb interactions could participate in the SCR reaction and easily consume NH4+ from the deposited ABS on the catalyst. These were the main reasons for promoting SCR performances and ABS resistance of Cu-KIT-6 nanoporous catalysts by Nb modification. Such findings could pave a way for the development of highly efficient SCR catalysts with good ABS resistance for real application.
{"title":"Unveiling the Promoting Effect of Niobium on Cu-KIT-6 Nanoporous Catalysts for the Selective Catalytic Reduction of NOx with High Resistance to Ammonium Bisulfate Poisoning","authors":"Zhanpeng Luo, Wenhua Wang, Shumei Gao, Guohua Zhao, Xiaoqiang Wang","doi":"10.1021/acsanm.4c02420","DOIUrl":"https://doi.org/10.1021/acsanm.4c02420","url":null,"abstract":"In this study, Nb modification was applied to promote the performance of selective catalytic reduction (SCR) of NO<sub><i>x</i></sub> and NH<sub>4</sub>HSO<sub>4</sub> (ABS) resistance of pure silica molecular sieve KIT-6-supported copper nanoporous catalysts. Experimental results revealed that the optimal Cu<sub>5</sub>–NK sample possessed above 80% deNO<sub><i>x</i></sub> efficiency with good N<sub>2</sub> selectivity in the temperature range of 260–400 °C and ABS deposition only reduced the SCR efficiency of the Cu<sub>5</sub>–NK sample by 20% at 320 °C. Characterization results indicated that Nb modification would induce formation of strong interactions with Cu, which enlarged pore size, amplified dispersion of active Cu species, and enhanced redox ability and surface acidity. Importantly, the enlarged pore size could weaken the thermal stability of ABS and promote its decomposition, while more active Cu sites retained by strong Cu–Nb interactions could participate in the SCR reaction and easily consume NH<sub>4</sub><sup>+</sup> from the deposited ABS on the catalyst. These were the main reasons for promoting SCR performances and ABS resistance of Cu-KIT-6 nanoporous catalysts by Nb modification. Such findings could pave a way for the development of highly efficient SCR catalysts with good ABS resistance for real application.","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":null,"pages":null},"PeriodicalIF":5.9,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141525265","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}
Nickel-based sulfides have been proven to be excellent oxygen evolution reaction (OER) electrocatalysts due to their excellent electrical conductivity, but their poor stability hinders their application in practical applications. To address this issue, defect engineering has been proposed as a viable strategy to enhance the electronic structure of the catalyst and further boost the OER performance. Herein, a MOF-derived Sn-doped NiS/Ni3S2 nanostructure grown in situ on nickel foam (Sn–NixSy/NF) has been designed as an active OER electrocatalyst. The morphology of the material was significantly impacted by the addition of the Sn elements, nanorods modified with nanoparticles providing more active sites. Moreover, the introduction of Sn elements induced the generation of sulfur vacancies (Vs), enhanced electron transfer, promoted electron redistribution, and increased the charge transfer rate. All of these endow the Sn–NixSy/NF-T with exceptionally low overpotentials of 104 and 286 mV to achieve a current density of 10 and 100 mA cm–2 for OER. Moreover, the Sn–NixSy/NF-T showed long-term stability, maintaining 100 h at current densities of 100 mA cm–2. In short, this work opened a route for engineering defects to boost the OER.
镍基硫化物因其出色的导电性而被证明是极佳的氧进化反应（OER）电催化剂，但其较差的稳定性阻碍了其在实际应用中的应用。为解决这一问题，有人提出了缺陷工程这一可行的策略，以增强催化剂的电子结构，进一步提高 OER 性能。在此，我们设计了一种在镍泡沫上原位生长的掺杂 Sn 的 MOF 衍生 NiS/Ni3S2 纳米结构（Sn-NixSy/NF），作为一种活性 OER 电催化剂。锡元素的加入对材料的形态产生了显著影响，纳米颗粒修饰的纳米棒提供了更多的活性位点。此外，锡元素的引入诱导了硫空位（Vs）的产生，增强了电子转移，促进了电子再分布，并提高了电荷转移速率。所有这些都赋予了 Sn-NixSy/NF-T 104 mV 和 286 mV 的超低过电位，使 OER 的电流密度分别达到 10 mA 和 100 mA cm-2。此外，Sn-NixSy/NF-T 还具有长期稳定性，在 100 mA cm-2 的电流密度下可维持 100 小时。总之，这项工作为利用工程缺陷提高 OER 开辟了一条途径。
{"title":"Defect Engineering in Sn-Doped NiS/Ni3S2 Nanostructures for Oxygen Evolution Reaction","authors":"Chunxiao Li, Yuying Feng, Jiahui Jiang, Jingjing Zhu, Heju Gao, Ting Zhao, Guancheng Xu, Li Zhang","doi":"10.1021/acsanm.4c02251","DOIUrl":"https://doi.org/10.1021/acsanm.4c02251","url":null,"abstract":"Nickel-based sulfides have been proven to be excellent oxygen evolution reaction (OER) electrocatalysts due to their excellent electrical conductivity, but their poor stability hinders their application in practical applications. To address this issue, defect engineering has been proposed as a viable strategy to enhance the electronic structure of the catalyst and further boost the OER performance. Herein, a MOF-derived Sn-doped NiS/Ni<sub>3</sub>S<sub>2</sub> nanostructure grown in situ on nickel foam (Sn–Ni<sub><i>x</i></sub>S<sub><i>y</i></sub>/NF) has been designed as an active OER electrocatalyst. The morphology of the material was significantly impacted by the addition of the Sn elements, nanorods modified with nanoparticles providing more active sites. Moreover, the introduction of Sn elements induced the generation of sulfur vacancies (V<sub>s</sub>), enhanced electron transfer, promoted electron redistribution, and increased the charge transfer rate. All of these endow the Sn–Ni<sub><i>x</i></sub>S<sub><i>y</i></sub>/NF-T with exceptionally low overpotentials of 104 and 286 mV to achieve a current density of 10 and 100 mA cm<sup>–2</sup> for OER. Moreover, the Sn–Ni<sub><i>x</i></sub>S<sub><i>y</i></sub>/NF-T showed long-term stability, maintaining 100 h at current densities of 100 mA cm<sup>–2</sup>. In short, this work opened a route for engineering defects to boost the OER.","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":null,"pages":null},"PeriodicalIF":5.9,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141525348","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}
The application of BiVO4 in photoelectrochemical water splitting for efficient clean hydrogen energy production encounters challenges arising from the sluggish kinetics of water oxidation. Motivated by the synergistic interplay of metal sites and ligands on the catalyst surface, we utilized the photoelectric deposition technique to introduce amorphous nanothin layers of cobalt–iron double hydroxide (referred to as CoFe-LDH) onto the Fe-doped BiVO4 surface. Fe dopants lead to a size reduction of BiVO4 nanoparticles while enlarging the specific surface area and pore volume, thus increasing the reaction sites, which is favorable for photoelectrochemical water splitting. The unique dual-layered structure of CoFe-LDH not only enhances the mobility of charge carriers but also addresses surface defects through passivation. Additionally, it optimizes the exposure of active sites on the surface and expedites the flow of charge carriers, effectively mitigating recombination. The CoFe/Fe-BiVO4 photoanode demonstrates outstanding photocatalytic performance, achieving a substantial photocurrent of 2.56 mA cm–2 (at 1.23 V vs RHE) and an impressive incident photon current conversion efficiency (IPCE) of 52.1% at 400 nm, which is approximately a 270% increment in photocurrent and a remarkable 2.2-fold improvement in IPCE compared to those of the unmodified sample. In addition, the charge surface transport efficiency increases from 16.8% to 62.5% at 1.23 V vs RHE after modification of the cobalt–iron hydroxide bilayer. This study not only emphasizes the promising results of employing binary polymetallic co-catalysts but also provides a strategic pathway to improve semiconductor-based photoelectrodes in various photoelectrochemical applications.
{"title":"CoFe Layered Double Hydroxide Supported on Fe-Doped BiVO4 Nanoparticles as Photoanode for Photoelectrochemical Water Splitting","authors":"Meihong Chen, Xiaobo Chang, Zhuangzhuang Ma, Xiaotong Gao, Lichao Jia","doi":"10.1021/acsanm.4c02041","DOIUrl":"https://doi.org/10.1021/acsanm.4c02041","url":null,"abstract":"The application of BiVO<sub>4</sub> in photoelectrochemical water splitting for efficient clean hydrogen energy production encounters challenges arising from the sluggish kinetics of water oxidation. Motivated by the synergistic interplay of metal sites and ligands on the catalyst surface, we utilized the photoelectric deposition technique to introduce amorphous nanothin layers of cobalt–iron double hydroxide (referred to as CoFe-LDH) onto the Fe-doped BiVO<sub>4</sub> surface. Fe dopants lead to a size reduction of BiVO<sub>4</sub> nanoparticles while enlarging the specific surface area and pore volume, thus increasing the reaction sites, which is favorable for photoelectrochemical water splitting. The unique dual-layered structure of CoFe-LDH not only enhances the mobility of charge carriers but also addresses surface defects through passivation. Additionally, it optimizes the exposure of active sites on the surface and expedites the flow of charge carriers, effectively mitigating recombination. The CoFe/Fe-BiVO<sub>4</sub> photoanode demonstrates outstanding photocatalytic performance, achieving a substantial photocurrent of 2.56 mA cm<sup>–2</sup> (at 1.23 V vs RHE) and an impressive incident photon current conversion efficiency (IPCE) of 52.1% at 400 nm, which is approximately a 270% increment in photocurrent and a remarkable 2.2-fold improvement in IPCE compared to those of the unmodified sample. In addition, the charge surface transport efficiency increases from 16.8% to 62.5% at 1.23 V vs RHE after modification of the cobalt–iron hydroxide bilayer. This study not only emphasizes the promising results of employing binary polymetallic co-catalysts but also provides a strategic pathway to improve semiconductor-based photoelectrodes in various photoelectrochemical applications.","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":null,"pages":null},"PeriodicalIF":5.9,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141525262","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}
In recent years, the pursuit of luminescent thermometer probes with low cost and high sensitivity has become a significant research challenge. This work proposes a strategy that employs lanthanide ions and carbon dots with dual-emission with diverse temperature dependencies to achieve high-temperature sensitivity. Specifically, the fabrication of dual-activated temperature probes has been achieved using NaMgF3:Eu3+/carbon dot nanocomposites through a simple coprecipitation process at room temperature. The optical temperature sensor, NaMgF3:Eu3+/carbon dot, was developed using Eu3+ emission as an internal standard and carbon dot as the temperature signal. The sensor exhibits a substantial absolute sensitivity of 8.3 ± 0.2%K–1 and a relative sensitivity of 2.0 ± 0.1%K–1, both at 300 K, making it a promising candidate for physiological thermometry. Within the temperature range of 300–440 K, the NaMgF3:Eu3+/carbon dot probe shows a relative sensitivity of better than 1.0%K–1 with good excellent repeatability as well as a nearly linear relationship between the Commission Internationale de l’Echlairage chromaticity coordinates of the observed fluorescent color change. The feasibility of the proposed strategy has also been verified by modifying lanthanide ions, e.g., Tb3+. It is anticipated that this pilot study will serve as a springboard for research on dual-mode nanothermometers with superior ratiometric and colorimetric performance.
{"title":"Developing Luminescent Ratiometric Thermometers Based on Dual-Emission of NaMgF3:Eu3+/Carbon Dot Nanocomposites","authors":"Rui Li, Xiaoyi Wu, Yeqing Chen, Qingguang Zeng, Tingting Deng, Ting Yu","doi":"10.1021/acsanm.4c02103","DOIUrl":"https://doi.org/10.1021/acsanm.4c02103","url":null,"abstract":"In recent years, the pursuit of luminescent thermometer probes with low cost and high sensitivity has become a significant research challenge. This work proposes a strategy that employs lanthanide ions and carbon dots with dual-emission with diverse temperature dependencies to achieve high-temperature sensitivity. Specifically, the fabrication of dual-activated temperature probes has been achieved using NaMgF<sub>3</sub>:Eu<sup>3+</sup>/carbon dot nanocomposites through a simple coprecipitation process at room temperature. The optical temperature sensor, NaMgF<sub>3</sub>:Eu<sup>3+</sup>/carbon dot, was developed using Eu<sup>3+</sup> emission as an internal standard and carbon dot as the temperature signal. The sensor exhibits a substantial absolute sensitivity of 8.3 ± 0.2%K<sup>–1</sup> and a relative sensitivity of 2.0 ± 0.1%K<sup>–1</sup>, both at 300 K, making it a promising candidate for physiological thermometry. Within the temperature range of 300–440 K, the NaMgF<sub>3</sub>:Eu<sup>3+</sup>/carbon dot probe shows a relative sensitivity of better than 1.0%K<sup>–1</sup> with good excellent repeatability as well as a nearly linear relationship between the Commission Internationale de l’Echlairage chromaticity coordinates of the observed fluorescent color change. The feasibility of the proposed strategy has also been verified by modifying lanthanide ions, e.g., Tb<sup>3+</sup>. It is anticipated that this pilot study will serve as a springboard for research on dual-mode nanothermometers with superior ratiometric and colorimetric performance.","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":null,"pages":null},"PeriodicalIF":5.9,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141525268","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}
Rajkumar Sahoo, Nayana Mukherjee, Sanchita Paramanik, Nikhil R. Jana
Pickering emulsions are attractive carriers and platforms in the cosmetic, food, and biomedical industries. However, their application as delivery carriers is restricted due to their larger size and premature cargo release. Here, we show that Pickering nanoemulsion of 200–300 nm size can be used as drug delivery carriers by a nonendocytic approach via the fusion of oil droplets with cell membranes. We found that this unique delivery feature offers enhanced cytosolic delivery of camptothecin along with predominant cell nucleus targeting that leads to 10 times enhanced therapeutic performance. The driving forces for this nonendocytic delivery are the large size of Pickering nanoemulsions that restricts their endocytic uptake, unique surface chemistry of stabilizer nanoparticles that induces attachment with the cell membrane, and noncompact surface of nanoemulsions that allows fusion between oil droplets and the membrane followed by delivery of the drug from the droplet interior into the cytosol. The presented approach can be adapted for drug delivery to cells via nonendocytic approach with enhanced therapeutic performance.
{"title":"Vegetable Oil–Based Pickering Nanoemulsions As Carriers for Cytosolic Drug Delivery","authors":"Rajkumar Sahoo, Nayana Mukherjee, Sanchita Paramanik, Nikhil R. Jana","doi":"10.1021/acsanm.4c02757","DOIUrl":"https://doi.org/10.1021/acsanm.4c02757","url":null,"abstract":"Pickering emulsions are attractive carriers and platforms in the cosmetic, food, and biomedical industries. However, their application as delivery carriers is restricted due to their larger size and premature cargo release. Here, we show that Pickering nanoemulsion of 200–300 nm size can be used as drug delivery carriers by a nonendocytic approach via the fusion of oil droplets with cell membranes. We found that this unique delivery feature offers enhanced cytosolic delivery of camptothecin along with predominant cell nucleus targeting that leads to 10 times enhanced therapeutic performance. The driving forces for this nonendocytic delivery are the large size of Pickering nanoemulsions that restricts their endocytic uptake, unique surface chemistry of stabilizer nanoparticles that induces attachment with the cell membrane, and noncompact surface of nanoemulsions that allows fusion between oil droplets and the membrane followed by delivery of the drug from the droplet interior into the cytosol. The presented approach can be adapted for drug delivery to cells via nonendocytic approach with enhanced therapeutic performance.","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":null,"pages":null},"PeriodicalIF":5.9,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141525344","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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