Shixun Hu, Cheng Tong, Xiongjie Yang, Shangshi Huang, Jun Hu, Qi Li, Jinliang He
As a rather effective method to enhance the dielectric performance of polyolefin materials, polar side group modification has been extensively applied in the insulation and energy storage materials in electrical and electronic systems. This work adopts two side groups with different topological structure, namely vinyl acetate (VAc, aliphatic chain) and N-vinyl-pyrrolidone (NVP, saturated ring) to chemically grafting-modify polypropylene (PP), and studies how the structural topology of polar side group affects the microscopic and macroscopic characteristics of PP, particularly the electrical anti-breakdown ability. Experimental results show that the side group structural topology can directly affect the crystallization and thermal properties of PP. Whilst the in-depth computational analysis indicates the grafted NVP possesses lower deep trap depth than VAc, which is connected with the topological structure and corresponding orbital interaction within the side group. Furthermore, molecular dynamics (MD) simulation reveals the saturated ring in NVP side group leads to more free volume within the material condensed state than VAc. Therefore by contrast, VAc-grafted PP with deeper trap orbitals and less free volume exhibits higher breakdown strength enhancement up to 21% and 14% under 30 and 90 °C, respectively. This work provides a novel understanding upon the topological structure effect of side group on the macroscopic dielectric performance from the view of microscopic physical chemistry, and would be referable for the refined design and properties modulation of dielectric materials in modern electrical power facilities.
{"title":"Side group topological structure modified orbital and condensed state characteristics enhance the electrical anti-breakdown performance of polyolefin","authors":"Shixun Hu, Cheng Tong, Xiongjie Yang, Shangshi Huang, Jun Hu, Qi Li, Jinliang He","doi":"10.1039/d4cp03902e","DOIUrl":"https://doi.org/10.1039/d4cp03902e","url":null,"abstract":"As a rather effective method to enhance the dielectric performance of polyolefin materials, polar side group modification has been extensively applied in the insulation and energy storage materials in electrical and electronic systems. This work adopts two side groups with different topological structure, namely vinyl acetate (VAc, aliphatic chain) and N-vinyl-pyrrolidone (NVP, saturated ring) to chemically grafting-modify polypropylene (PP), and studies how the structural topology of polar side group affects the microscopic and macroscopic characteristics of PP, particularly the electrical anti-breakdown ability. Experimental results show that the side group structural topology can directly affect the crystallization and thermal properties of PP. Whilst the in-depth computational analysis indicates the grafted NVP possesses lower deep trap depth than VAc, which is connected with the topological structure and corresponding orbital interaction within the side group. Furthermore, molecular dynamics (MD) simulation reveals the saturated ring in NVP side group leads to more free volume within the material condensed state than VAc. Therefore by contrast, VAc-grafted PP with deeper trap orbitals and less free volume exhibits higher breakdown strength enhancement up to 21% and 14% under 30 and 90 °C, respectively. This work provides a novel understanding upon the topological structure effect of side group on the macroscopic dielectric performance from the view of microscopic physical chemistry, and would be referable for the refined design and properties modulation of dielectric materials in modern electrical power facilities.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"40 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912166","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Self-assembly of Nanoparticles (NPs) in solution has garnered tremendous attention among researchers because of their electrical, chemical, and optoelectronic properties at the macroscale with potential applications in bio-imaging, bio-medicine, and therapeutics. Control of size, shape, and composition at the nanoscale is important in tuning the material's bulk properties. The grafting of NPs with polymers enables us to tune such bulk material properties at the nano level by controlling their assemblies, especially in solutions. The stiffness of grafts plays a crucial role in tuning the self-assembly of spherical NPs grafted with polyions (PGNs). Many recent studies based on single-stranded DNA (ssDNA) and double-stranded DNA (dsDNA) showed the potential applications of such assemblies. In this work, we have performed coarse-grained molecular dynamics (MD) simulations to understand the charge-driven self-assembly of PGNs by varying stiffness of polymer grafts, the grafting density, and graft length. Self-assembly of these PGNs leads to the formation of different structures driven by the rigidity of polyion chains and the electrostatic interactions. A dramatic change in morphological transitions can be achieved, ranging from rings, strings, and percolated structures and ordered to disordered aggregates by tuning the control parameters. The percolated structures form disordered structures upon annealing with potential applications in thermal under filling, neuromorphic devices, and biological systems including drug delivery, and therapeutics.
{"title":"Role of polymer graft stiffness in electrostatic-driven self-assembly of nanoparticles in solutions","authors":"Rajesh Pavan Pothukuchi, Mithun Radhakrishna","doi":"10.1039/d4cp03669g","DOIUrl":"https://doi.org/10.1039/d4cp03669g","url":null,"abstract":"Self-assembly of Nanoparticles (NPs) in solution has garnered tremendous attention among researchers because of their electrical, chemical, and optoelectronic properties at the macroscale with potential applications in bio-imaging, bio-medicine, and therapeutics. Control of size, shape, and composition at the nanoscale is important in tuning the material's bulk properties. The grafting of NPs with polymers enables us to tune such bulk material properties at the nano level by controlling their assemblies, especially in solutions. The stiffness of grafts plays a crucial role in tuning the self-assembly of spherical NPs grafted with polyions (PGNs). Many recent studies based on single-stranded DNA (ssDNA) and double-stranded DNA (dsDNA) showed the potential applications of such assemblies. In this work, we have performed coarse-grained molecular dynamics (MD) simulations to understand the charge-driven self-assembly of PGNs by varying stiffness of polymer grafts, the grafting density, and graft length. Self-assembly of these PGNs leads to the formation of different structures driven by the rigidity of polyion chains and the electrostatic interactions. A dramatic change in morphological transitions can be achieved, ranging from rings, strings, and percolated structures and ordered to disordered aggregates by tuning the control parameters. The percolated structures form disordered structures upon annealing with potential applications in thermal under filling, neuromorphic devices, and biological systems including drug delivery, and therapeutics.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"81 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912168","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Due to the high light absorption coefficient, excellent electronic mobility, and the enhanced excitonic effect, two-dimensional (2D) GaN materials hold great potential for applications in optoelectronic and electronic devices. As metal-semiconductor junction (MSJ) is a fundamental component of semiconductor-based devices, identifying suitable metal for contacting with semiconductor is essential. In this work, detailed first-principles calculations are performed to investigate the contact behavior between GaN monolayer (ML) and a series of 2D metals MX2 (M = Nb, Ta, V, Mo, or W; X = S or Se). Despite the van der Waals (vdW) interface, Schottky barrier heights (SBHs) of MX2/GaN MSJs are found significantly deviated from the Schottky–Mott limit. Stronger and weaker Fermi level pinning effects are identified in higher and lower work function (WM) regions of metals, respectively. This is attributed to the asymmetric charge redistribution induced enhanced interface dipole (ΔP) in MSJs leading to the increased step potential (ΔV) as response of the increased WM of MX2. P-type quasi-Ohmic contact could be realized in Ga-top stacking H-TaS2/GaN, H-NbS2/GaN, and H-VS2/GaN, indicating the potential application of 2D H-TaS2, H-NbS2, and H-VS2 as electrode materials. Appling biaxial tensile strain is identified to be a feasible strategy for modulating the contact behavior in MX2/GaN, as it could effectively tune the SBH, change the contact type, or induce Schottky to quasi-Ohmic contact transition. We demonstrate that strain effects on the contact properties of MX2/GaN MSJs are both MX2 and stacking configuration dependent, which are determined by the synergistic effect of strain-modulated ionization energy and electron affinity of GaN ML, WM of MX2, and ΔV- and ΔP-quantified interface coupling in MSJs. Our work not only offers insights for prospection into the fundamental contact properties of 2D metal/GaN vdW interfaces, but also provides electrode material selection and strain strategies to achieve Ohmic contact as well as tunable SBHs in 2D GaN, which helps give theoretical guidance for developing high-performance 2D GaN-based optoelectronic and electronic devices.
{"title":"2D Metallic Transition Metal Dichalcogenides: Promising Contact Metals for 2D GaN-Based (Opto)electronic Devices","authors":"Jing Li, Lei Ao, Zhihua Xiong","doi":"10.1039/d4cp03794d","DOIUrl":"https://doi.org/10.1039/d4cp03794d","url":null,"abstract":"Due to the high light absorption coefficient, excellent electronic mobility, and the enhanced excitonic effect, two-dimensional (2D) GaN materials hold great potential for applications in optoelectronic and electronic devices. As metal-semiconductor junction (MSJ) is a fundamental component of semiconductor-based devices, identifying suitable metal for contacting with semiconductor is essential. In this work, detailed first-principles calculations are performed to investigate the contact behavior between GaN monolayer (ML) and a series of 2D metals MX<small><sub>2</sub></small> (M = Nb, Ta, V, Mo, or W; X = S or Se). Despite the van der Waals (vdW) interface, Schottky barrier heights (SBHs) of MX<small><sub>2</sub></small>/GaN MSJs are found significantly deviated from the Schottky–Mott limit. Stronger and weaker Fermi level pinning effects are identified in higher and lower work function (W<small><sub>M</sub></small>) regions of metals, respectively. This is attributed to the asymmetric charge redistribution induced enhanced interface dipole (Δ<em>P</em>) in MSJs leading to the increased step potential (ΔV) as response of the increased W<small><sub>M</sub></small> of MX<small><sub>2</sub></small>. P-type quasi-Ohmic contact could be realized in Ga-top stacking H-TaS<small><sub>2</sub></small>/GaN, H-NbS<small><sub>2</sub></small>/GaN, and H-VS<small><sub>2</sub></small>/GaN, indicating the potential application of 2D H-TaS<small><sub>2</sub></small>, H-NbS<small><sub>2</sub></small>, and H-VS<small><sub>2</sub></small> as electrode materials. Appling biaxial tensile strain is identified to be a feasible strategy for modulating the contact behavior in MX<small><sub>2</sub></small>/GaN, as it could effectively tune the SBH, change the contact type, or induce Schottky to quasi-Ohmic contact transition. We demonstrate that strain effects on the contact properties of MX<small><sub>2</sub></small>/GaN MSJs are both MX<small><sub>2</sub></small> and stacking configuration dependent, which are determined by the synergistic effect of strain-modulated ionization energy and electron affinity of GaN ML, W<small><sub>M</sub></small> of MX<small><sub>2</sub></small>, and ΔV- and Δ<em>P</em>-quantified interface coupling in MSJs. Our work not only offers insights for prospection into the fundamental contact properties of 2D metal/GaN vdW interfaces, but also provides electrode material selection and strain strategies to achieve Ohmic contact as well as tunable SBHs in 2D GaN, which helps give theoretical guidance for developing high-performance 2D GaN-based optoelectronic and electronic devices.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"43 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912171","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Reasonable design of hydrogen evolution reaction (HER) electrocatalysts with low Pt loading and excellent catalytic performance is a key challenge in finding efficient and cost attractive catalysts. Pt with unique d-electron, which provides new opportunities for the development of HER catalysts when it forms compounds with C of high abundance on earth. Here, focusing on designing highly efficient catalysts composed of Pt and C elements by first-principles structure search simulations, identifying four stability PtCx monolayers. The novel PtC monolayer with zigzag C chain not only possesses lower Pt loading, but also shows inherent metallicity. Meanwhile, its H2O adsorption and dissociation abilities are efficient and easy. The HER activity of the PtC monolayer is comparable to the commercial Pt, e.g. desirable ΔGH* values and larger exchange current density, mainly attributing to lower charge donated of Pt, larger occupation of Pt PDOS at the Fermi level, and pair electrons of zigzag C chain. Moreover, its excellent HER activity can be maintained even at high H coverage under strain and solvent effect. All these attractive properties render the PtC monolayer an appropriate HER catalyst.
{"title":"Metallic PtC monolayer as a promising hydrogen evolution electrocatalyst","authors":"Huan Lou, Chi Ma","doi":"10.1039/d4cp04355c","DOIUrl":"https://doi.org/10.1039/d4cp04355c","url":null,"abstract":"Reasonable design of hydrogen evolution reaction (HER) electrocatalysts with low Pt loading and excellent catalytic performance is a key challenge in finding efficient and cost attractive catalysts. Pt with unique d-electron, which provides new opportunities for the development of HER catalysts when it forms compounds with C of high abundance on earth. Here, focusing on designing highly efficient catalysts composed of Pt and C elements by first-principles structure search simulations, identifying four stability PtCx monolayers. The novel PtC monolayer with zigzag C chain not only possesses lower Pt loading, but also shows inherent metallicity. Meanwhile, its H2O adsorption and dissociation abilities are efficient and easy. The HER activity of the PtC monolayer is comparable to the commercial Pt, e.g. desirable ΔGH* values and larger exchange current density, mainly attributing to lower charge donated of Pt, larger occupation of Pt PDOS at the Fermi level, and pair electrons of zigzag C chain. Moreover, its excellent HER activity can be maintained even at high H coverage under strain and solvent effect. All these attractive properties render the PtC monolayer an appropriate HER catalyst.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"14 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912163","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ángel Martín Pendás, Diogo J. L. Rodrigues, Evelio Francisco
A claim that ionic bonds exist only in ionic solids is critically analyzed by focusing on the controversial LiH molecule, classified as covalent by non-orthogonal valence bond supporters, polar-covalent by molecular orbital advocates, and ionic by real-space proponents. Using orbital invariant techniques we show that LiH can be regarded ionic in the same manner as dihydrogen covalent.
{"title":"Can we talk about ionic bonds in molecules? Yes, just as we do for covalent bonds†","authors":"Ángel Martín Pendás, Diogo J. L. Rodrigues, Evelio Francisco","doi":"10.1039/d4cp04353g","DOIUrl":"https://doi.org/10.1039/d4cp04353g","url":null,"abstract":"A claim that ionic bonds exist only in ionic solids is critically analyzed by focusing on the controversial LiH molecule, classified as covalent by non-orthogonal valence bond supporters, polar-covalent by molecular orbital advocates, and ionic by real-space proponents. Using orbital invariant techniques we show that LiH can be regarded ionic in the same manner as dihydrogen covalent.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"115 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912172","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This study theoretically investigates the defect-related electronic structure and transport properties in a device where a semiconductor bilayer SnS2 (BL-SnS2) serves as the central scattering region and bilayer SnS2 with cobalt atoms intercalation (Co-SnS2) as metallic electrodes. The Co-SnS2/BL-SnS2 junction forms an ohmic contact, which is robust to defects. Low contact resistance of 52.1 Ω·μm and 56.2 Ω·μm are obtained in the zigzag (ZZ) and armchair (AC) transport directions, respectively. Defects, whether near the interface or in the middle of the central region, reduce the barrier between metal and semiconductor and the contact resistance. In particular, defects in the middle of the central region introduce impurity states and may result in resonant tunneling processes. It causes leakage current in the AC direction but not in the ZZ direction because impurity-associated transmission peaks in the latter are always outside the bias window.
{"title":"Effect of defects on ballistic transport in a bilayer SnS2 based junction with Co intercalated electrodes","authors":"Miao Liu, Huan Wang, Xiaojie Liu, Yin Wang, Haitao Yin","doi":"10.1039/d4cp03605k","DOIUrl":"https://doi.org/10.1039/d4cp03605k","url":null,"abstract":"This study theoretically investigates the defect-related electronic structure and transport properties in a device where a semiconductor bilayer SnS2 (BL-SnS2) serves as the central scattering region and bilayer SnS2 with cobalt atoms intercalation (Co-SnS2) as metallic electrodes. The Co-SnS2/BL-SnS2 junction forms an ohmic contact, which is robust to defects. Low contact resistance of 52.1 Ω·μm and 56.2 Ω·μm are obtained in the zigzag (ZZ) and armchair (AC) transport directions, respectively. Defects, whether near the interface or in the middle of the central region, reduce the barrier between metal and semiconductor and the contact resistance. In particular, defects in the middle of the central region introduce impurity states and may result in resonant tunneling processes. It causes leakage current in the AC direction but not in the ZZ direction because impurity-associated transmission peaks in the latter are always outside the bias window.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"14 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912269","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Magnetic semiconductors with spin-polarized non-metallic atoms are usually ignored in applications because of their poor performances in magnetic moments and critical temperatures. Here, magnetic characteristics of 2D pentagon-based XN2 (X = B, Al, Ga) are revealed based on first-principles calculations. It has been proved that XN2 are antiferromagnetic semiconductors with bandgaps of 2.15 eV, 2.42 eV and 2.16 eV respectively. Through analyses of spin density distributions and molecular orbitals, magnetic origin is located at the antibonding orbitals (π*2px and π*2pz) of covalently bonded N atoms. Furthermore, it has also been demonstrated that XN2 have Néel temperatures (TN) of as high as 136 K, 266 K and 477 K through Monte Carlo (MC) simulations of the Ising model. More significantly, the phase transition of magnetic ground state from antiferromagnetic order to ferromagnetic order, continuous distribution of bandgaps from 2.0 eV to 2.5 eV, and enhancement of magnetic moment from 0.3 µB to 1.2 µB can be realized by exerting external fields. Our work proposes a novel spin-polarized phenomenon based on the covalent bond, ameliorating the performances of magnetic semiconductors with spin-polarized p orbit electrons and providing immense application potentials for XN2 in spintronic devices.
{"title":"High Néel temperature and magnetism modulation in 2D pentagon-based structures XN2 (X = B, Al, Ga) with spin-polarized non-metallic atoms","authors":"Zhenyu Wu, Hong Zhang","doi":"10.1039/d4cp04582c","DOIUrl":"https://doi.org/10.1039/d4cp04582c","url":null,"abstract":"Magnetic semiconductors with spin-polarized non-metallic atoms are usually ignored in applications because of their poor performances in magnetic moments and critical temperatures. Here, magnetic characteristics of 2D pentagon-based XN2 (X = B, Al, Ga) are revealed based on first-principles calculations. It has been proved that XN2 are antiferromagnetic semiconductors with bandgaps of 2.15 eV, 2.42 eV and 2.16 eV respectively. Through analyses of spin density distributions and molecular orbitals, magnetic origin is located at the antibonding orbitals (π*2px and π*2pz) of covalently bonded N atoms. Furthermore, it has also been demonstrated that XN2 have Néel temperatures (TN) of as high as 136 K, 266 K and 477 K through Monte Carlo (MC) simulations of the Ising model. More significantly, the phase transition of magnetic ground state from antiferromagnetic order to ferromagnetic order, continuous distribution of bandgaps from 2.0 eV to 2.5 eV, and enhancement of magnetic moment from 0.3 µB to 1.2 µB can be realized by exerting external fields. Our work proposes a novel spin-polarized phenomenon based on the covalent bond, ameliorating the performances of magnetic semiconductors with spin-polarized p orbit electrons and providing immense application potentials for XN2 in spintronic devices.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"179 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142905315","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jiangfang Wang, Yang Xu, Anqi Wei, Julian Skagfjörd Reinhold, Lixin Wei, Lei Shi, Yushuo Zhang, Song Liu, Chong Wang, Bo Zhang
We have constructed a series of model metal phthalocyanine (MPc) for the carbon dioxide reduction reaction (CO2RR), constructed a volcano relationship through density functional theory (DFT) and experiments, and obtained cobalt phthalocyanine (COPC) at the apex. The volcano diagram is conducive to the screening of catalysts and has a guiding role in the design of catalysts.
{"title":"The Volcanic Relationship of Model Molecular Catalysts in CO2 Reduction Reaction","authors":"Jiangfang Wang, Yang Xu, Anqi Wei, Julian Skagfjörd Reinhold, Lixin Wei, Lei Shi, Yushuo Zhang, Song Liu, Chong Wang, Bo Zhang","doi":"10.1039/d4cp03912b","DOIUrl":"https://doi.org/10.1039/d4cp03912b","url":null,"abstract":"We have constructed a series of model metal phthalocyanine (MPc) for the carbon dioxide reduction reaction (CO2RR), constructed a volcano relationship through density functional theory (DFT) and experiments, and obtained cobalt phthalocyanine (COPC) at the apex. The volcano diagram is conducive to the screening of catalysts and has a guiding role in the design of catalysts.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"20 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142905317","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The combination of plasmonic metals and Mxene, as a new and interesting member of the 2D material class, may provide unique advantages in terms of low cost, versatility, flexibility, and improved activity as an ideal surface-enhanced Raman spectroscopy (SERS) platform. Despite the recent progress, the present studies on the utilization of plasmonic metal/Mxene-based SERS systems are quite limited and cannot benefit from the extraordinary properties of this combination. In this study, for the first time, we propose the layer-by-layer (LbL) thin film of Ti3C2 MXene and gold nanoparticles (AuNPs) as a robust SERS platform (Ti3C2/AuNPs). For this, Ti3C2 MXene was synthesized from the Ti3AlC2 MAX phase, and Ti3C2/AuNPs LbL film was fabricated via the vacuum-assisted filtration method to create consecutive layers of each material. This procedure produced densely distributed AuNPs in the LbL film in a well-controlled manner. The SERS activity tests for methylene blue and DTNB as Raman reporter molecules showed that they had 1.5 × 106 and 1.2 × 106 enhancement factors and 1 × 10-8 M, and 2.5 × 10-8 M limits of detection, respectively. Various mechanisms, including the formation of hotspots due to AuNPs on the interlayer of Ti3C2, improved surface roughness and resultant optical activity, as well as the synergistic effect between Ti3C2 and AuNPs, contributed to the resultant SERS activity to some extent. This study has proven the feasibility of the Ti3C2/AuNPs LbL system as a robust SERS-based sensor platform, paving the way for its use in various biological and chemical applications.
{"title":"Layer-by-layer Thin Film of Ti3C2 MXene and Gold Nanoparticles as an Ideal SERS Platform","authors":"Hayrunnisa Mazlumoglu, Mehmet Yilmaz","doi":"10.1039/d4cp01953a","DOIUrl":"https://doi.org/10.1039/d4cp01953a","url":null,"abstract":"The combination of plasmonic metals and Mxene, as a new and interesting member of the 2D material class, may provide unique advantages in terms of low cost, versatility, flexibility, and improved activity as an ideal surface-enhanced Raman spectroscopy (SERS) platform. Despite the recent progress, the present studies on the utilization of plasmonic metal/Mxene-based SERS systems are quite limited and cannot benefit from the extraordinary properties of this combination. In this study, for the first time, we propose the layer-by-layer (LbL) thin film of Ti3C2 MXene and gold nanoparticles (AuNPs) as a robust SERS platform (Ti3C2/AuNPs). For this, Ti3C2 MXene was synthesized from the Ti3AlC2 MAX phase, and Ti3C2/AuNPs LbL film was fabricated via the vacuum-assisted filtration method to create consecutive layers of each material. This procedure produced densely distributed AuNPs in the LbL film in a well-controlled manner. The SERS activity tests for methylene blue and DTNB as Raman reporter molecules showed that they had 1.5 × 106 and 1.2 × 106 enhancement factors and 1 × 10-8 M, and 2.5 × 10-8 M limits of detection, respectively. Various mechanisms, including the formation of hotspots due to AuNPs on the interlayer of Ti3C2, improved surface roughness and resultant optical activity, as well as the synergistic effect between Ti3C2 and AuNPs, contributed to the resultant SERS activity to some extent. This study has proven the feasibility of the Ti3C2/AuNPs LbL system as a robust SERS-based sensor platform, paving the way for its use in various biological and chemical applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"40 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142901888","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Shuang-Fei Zhu, Chaowen Yang, Shufen Zheng, Shu-hai Zhang, Ya-Hong Chen, Yang Liu
The initial decomposition reactions of 1,3,5-trinitrobenzene (TNB), picric acid (PA), 2,4,6-trinitrotoluene (TNT), 2,4,6-trinitroaniline (TNA) and 2,4,6-trinitrophenylmethylnitramine (Tetryl) were studied using ReaxFF-lg molecular dynamics simulations, and the substituents effect on the thermal decomposition behaviours of nitrobenzene compounds was evaluated through the reactant number, initial decomposition pathway, products and cluster analysis. Results showed that the introduction of substituents could promote the decomposition of reactants, increase the frequency of nitro-nitrito isomerization reaction and intermolecular H or O atom transfer reaction, and reduce the frequency of direct nitro dissociation reaction. Notably, these effects were most obvious in the case of TNT. Owing to the introduction of substituents, the number of hydrogen-containing products (HO2N, H2, H2O and NH3) increased. Different functional groups can also lead to variations in the quantities of decomposition products and clusters distribution. The decomposition process of the five nitrobenzenes were detailed examined through the analysis of intermediate products, revealing the distinct influence of the substituent groups. These findings contribute to an enhanced understanding of how different substituent groups influence the energy release mechanisms of energetic compounds.
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