arXiv subjects

Guosheng Shi

Publications and source records attributed to Guosheng Shi.

16 recordsLinked to original sources

arXiv2025

Double-Layered Silica-Engineered Fluorescent Nanodiamonds for Catalytic Generation and Quantum Sensing of Active Radicals

Fluorescent nanodiamonds (FNDs) hosting nitrogen-vacancy (NV) centers have attracted considerable attention for quantum sensing applications, particularly owing to notable advancements achieved in the field of weak magnetic signal detection in recent years. Here, we report a practical quantum-sensing platform for the controlled production and real-time monitoring of ultra-short-lived reactive free radicals using a double-layered silica modification strategy. An inner dense silica layer preserves the intrinsic properties of NV centers, while an outer porous silica layer facilitates efficient adsorption and stabilization of hydroxyl radicals and their precursor reactants. By doping this mesoporous shell with gadolinium (III) catalysts, we achieve sustained, light-free generation of hydroxyl radicals via catalytic water splitting, eliminating reliance on external precursors. The mechanism underlying this efficient radical generation is discussed in detail. The radical production is monitored in real time and in situ through spin-dependent T1 relaxometry of the NV centers, demonstrating stable and tunable radical fluxes, with concentration tunable across a continuous range from approximately 100 mM to molar levels by adjusting the catalyst condition. This study extends the technical application of nanodiamonds from relaxation sensing to the controlled synthesis of reactive free radicals, thereby providing robust experimental evidence to support the advancement of quantum sensing systems in intelligent manufacturing.

quant-ph↗

arXiv2024

Electric imaging and dynamics of photo-charged graphene edge

The one-dimensional side gate based on graphene edges shows a significant capability of reducing the channel length of field-effect transistors, further increasing the integration density of semiconductor devices. The nano-scale electric field distribution near the edge provides the physical limit of the effective channel length, however, its imaging under ambient conditions still lacks, which is a critical aspect for the practical deployment of semiconductor devices. Here, we used scanning nitrogen-vacancy microscopy to investigate the electric field distribution near edges of a single-layer-graphene. Real-space scanning maps of photo-charged floating graphene flakes were acquired with a spatial resolution of $\sim$ 10 nm, and the electric edge effect was quantitatively studied by analyzing the NV spin energy level shifts due to the electric Stark effect. Since the graphene flakes are isolated from external electric sources, we brought out a theory based on photo-thermionic effect to explain the charge transfer from graphene to oxygen-terminated diamond probe with a disordered distribution of charge traps. Real-time tracing of electric fields detected the photo-thermionic emission process and the recombination process of the emitted electrons. This study provides a new perspective for graphene-based one-dimensional gates and opto-electronics with nanoscale real-space imaging, and moreover, offers a novel method to tune the chemical environment of diamond surfaces based on optical charge transfer.

cond-mat.mes-hall↗

arXiv2024

Wide-bandgap semiconductor of three-dimensional unconventional stoichiometric NaCl2 crystal

The expanding applications call for novel new-generation wide-bandgap semiconductors. Here, we show that a compound only composed of the ordinary elements Na and Cl, namely three-dimensional NaCl2 crystal, is a wide-bandgap semiconductor. This finding benefits from the breaking of conventional stoichiometry frameworks in the theoretical design, leading to the discovery of three-dimensional XY2 (X = Na, Li, K; Y = Cl, F, Br, I) crystals, with covalent bonds of Y pairs inducing the wide bandgap from 2.24 to 4.45 eV. Crucially, such an unexpected NaCl2 crystal was successfully synthesized under ambient conditions. The unconventional stoichiometric strategy with other chemical elements potentially yields more wide-bandgap semiconductors, offering the capability for bandgap tuning. These unconventional stoichiometric materials may also exhibit superconductivity, transparent inorganic electrides, high-energy-density, and beyond.

cond-mat.mtrl-sci↗

arXiv2024

Superconductivity of Bulk Abnormal Magic-stoichiometric Na3Cl Salt Crystals at Normal Pressure

The identification of new materials with superconducting properties is the pursuit in the realm of superconductivity research. Here, excitedly, we show that the simplest salt daily used can be made a superconductor at normal pressure only by adjusting its stoichiometry of Na and Cl as Na3Cl at normal pressure based on first-principles calculations. This bulk stable abnormal Na-Cl stoichiometric crystal of 3:1, the first 'magic' ratio, includes metallic (Na) atoms in the core as well as hybridization of ionic and metallic bonding, facilitating the electron-phonon-coupling for superconductivity with a critical temperature Tc of 0.13 K. The flat bands and van Hove singularities near the Fermi level produce large densities of states, similar to H3S and LaH10, which is beneficial for the emergence of superconductivity. The crystal composed of with abnormal Na-Cl magic stoichiometry is a precisely tunable, purely sodium and chloride-based, three-dimensional bulk superconductor, which is therefore an ideal material for designing and understanding abnormal stoichiometric crystals. The methodology of constructing this bulk abnormal crystal may be general to almost all elements, which could lead to insights into the physics of other conventional superconductors and even high-critical-temperature superconductors.

cond-mat.supr-con↗

arXiv2024

Room-temperature intrinsic ferromagnetism of two-dimensional Na2Cl crystals originated by s- and p-orbitals

Ferromagnetism, as one of the most valuable properties of materials, has attracted sustained and widespread interest in basic and applied research from ancient compasses to modern electronic devices. Traditionally, intrinsic ferromagnetism has been attributed to the permanent magnetic moment induced by partially filled d- or f-orbitals. However, the development of ferromagnetic materials has been limited by this electronic structure convention. Thus, the identification of additional materials that are not constrained by this conventional rule but also exhibit intrinsic ferromagnetism is highly expected and may impact all the fields based on ferromagnetism. Here, we report the direct observation of room-temperature intrinsic ferromagnetism in two-dimensional (2D) Na2Cl crystals, in which there are only partially filled s- and p-orbitals rather than d- or f-orbitals, using the superconducting quantum interference device (SQUID) and magnetic force microscope (MFM). These Na2Cl crystals formed in reduced graphene oxide (rGO) membranes have an unconventional stoichiometric structure leading to unique electron and spin distributions. And the structure of these 2D Na2Cl crystals, including the Na and Cl sites, is characterized in situ for the first time and directly observed by cryo-electron microscopy (cryo-EM) based on the observed difference in contrast between Na stacked with Cl and single Na. These findings break the conventional rule of intrinsic ferromagnetism and provide new insights into the design of novel magnetic and electronic devices and transistors with a size down to the atomic scale.

cond-mat.mtrl-sci↗

arXiv2022

Remarkably strong magnetic response in molecules with polar groups

For more than a century, electricity and magnetism have been believed to always exhibit inextricable link due to the symmetry in electromagnetism. At the interface, polar groups that have polar charges, are indispensable to be considered, which interact directly with other polar charges/external charges/external electric fields. However, there is no report on the corresponding magnetic properties on these polar groups. Clearly, such asymmetry, that is, only the interaction between the polar groups and charges, is out of bounds. Here we show that those molecules with considerable polar groups, such as cellulose acetate (CA) and other cellulose derivatives with different polar groups, can have strong magnetic response, indicating that they are strongly paramagnetic. Density functional theory (DFT) calculation shows that the polarity greatly reduces the excitation energy from the state without net spin (singlet) to the state with net spin (triplet), making the considerable existence of magnetic moments on the polar groups. We note that the hydrophobic groups in these molecules have no magnetic moments, however, they make the molecules aggregate to amply the magnetic effect of the magnetic moments in the polar groups, so that these magnetic moments can induce the strong paramagnetism. Our observations suggest a recovery of the symmetry with inextricable link between the electricity and magnetism at the interface. The findings leave many imaginations of the role of the magnetic interaction in biological systems as well as other magnetic applications considering that many of those polar materials are biological materials, pharmaceutical materials, chemical raw materials, and even an essential hormone in agricultural production.

cond-mat.soft↗

arXiv2021

Super strong paramagnetism induced by polar functional groups and water

We experimentally demonstrate that some commonly used materials such as cellulose acetate and chitin which are traditionally considered to be non-magnetic show super strong paramagnetism in aqueous solutions under ambient conditions when they are agglomerated by nanoparticles. Theoretical computations show that strongly polar functional groups can reduce the potential barrier for a singlet-triplet interconversion with the help of surrounding water, inducing the magnetic moments. These magnetic moments distributed on the surfaces of the nanoparticles, which make a large number of magnetic moments gather in a very small space, greatly enhance the alignment of the moments along and amplify the effect of the external magnetic field, resulting in the super strong paramagnetism. Our findings suggest that the polar functional group may always induce paramagnetism and the magnetic effect may be universal as the electric effects since the polarization is very common in materials.

cond-mat.soft↗

arXiv2020

Unexpectedly super strong paramagnetism of aromatic peptides due to cations of divalent metals

The magnetism of most biological systems has not been characterized, which directly impedes our understanding of many magnetic field-related phenomena, including magnetoreception and magnetic bio-effects. Here we measured the magnetic susceptibility of aromatic peptide AYFFF self-assemblies in the presence or absence of divalent metal cations in liquid phase at room temperature. Unexpectedly, the magnetic susceptibilities of AYFFF self-assemblies in the chloride solution of various divalent cations (Mg2+, Zn2+, and Cu2+) show super strong paramagnetism. We attribute the super strong paramagnetism to existence of the magnetic moments on the cations adsorbed on aromatic rings in the AYFFF assemblies through hydrated cation-π interactions, where the adsorbed cations display non-divalent behavior with unpaired electron spins. Our results indicate the super strong paramagnetism or potential ferromagnetism in the aromatic ring-enriched biomolecules when there are enough cations of divalent metals adsorbed. The findings not only provide fundamental information for understanding the magnetism of biological systems, provoke insights for investigating the origin of magnetoreception and bio-effects of magnetic fields, but also help developing future magnetic-control techniques on aromatic ring-enriched biomolecules and drugs in living organisms, as well as biomaterial fabrication and manipulation.

cond-mat.soft↗

arXiv2020

Remarkable antibacterial activity of reduced graphene oxide functionalized by copper ions

Despite long-term efforts for exploring antibacterial agents or drugs, it remains challenging how to potentiate antibacterial activity and meanwhile minimize toxicity hazards to the environment. Here, we experimentally show that the functionality of reduced graphene oxide (rGO) through copper ions displays selective antibacterial activity significantly stronger than that of rGO itself and no toxicity to mammalian cells. Remarkably, this antibacterial activity is two orders of magnitude greater than the activity of its surrounding copper ions. We demonstrate that the rGO is functionalized through the cation-$π$ interaction to massively adsorb copper ions to form a rGO-copper composite in solution and result in an extremely low concentration level of surrounding copper ions (less than ~0.5 $μM$). These copper ions on rGO are positively charged and strongly interact with negatively charged bacterial cells to selectively achieve antibacterial activity, while rGO exhibits the functionality to not only actuate rapid delivery of copper ions and massive assembly onto bacterial cells but also result in the valence shift in the copper ions from Cu$^{2+}$ into Cu$^{+}$ which greatly enhances the antibacterial activity. Notably, this functionality of rGO through cation-$π$ interaction with copper ions can similarly achieve algaecidal activity but does not exert cytotoxicity against neutrally charged mammalian cells. The remarkable selective antibacterial activity from the rGO functionality as well as the inherent broad-spectrum-antibacterial physical mechanism represents a significant step toward the development of a novel antibacterial material and reagent without environmental hazards for practical application.

physics.app-ph↗

arXiv2020

Enhanced water affinity of histidine by transition metal ions

Transitional metal ions widely exist in biological environments and are crucial to many life-sustaining physiological processes. Recently, transition metal ion such as Cu$^{2+}$, Zn$^{2+}$, Ni$^{2+}$, have been shown can increase the solubilities of aromatic biomolecules. Comparing with Cu$^{2+}$, Zn$^{2+}$ shows less enhancement to the solubilities of biomolecules such as tryptophan (Trp). On the other hand, Zn$^{2+}$ has a higher concentration in human blood plasma and appears in protein the most among transition metal ions, clarifying whether Zn$^{2+}$ can enhance the solubilities of other aromatic amino acids is significantly important. Herein, we observed that the solubility of aromatic amino acid histidine (His) is greatly enhanced in ZnCl$_2$ solution. Based on first principle calculations, this enhancement of solubility is attributed to cation-$π$ interaction between His and Zn$^{2+}$. Our results here are of great importance for the bioavailability of aromatic drugs and provide new insights for the understanding of physiological functions of Zn$^{2+}$.

physics.bio-ph↗

arXiv2019

Novel two-dimensional Ca-Cl crystals with metallicity, piezoelectric effect and room-temperature ferromagnetism

Recently we have reported the direct observation of two-dimensional (2D) Ca-Cl crystals on reduced graphene oxide (rGO) membranes, in which the calcium ions are only about monovalent (i.e. ~+1) and metallic rather than insulating properties are displayed by those CaCl crystals. Here, we report the experimental observation and demonstration of the formation of graphene-Ca-Cl heterojunction owing to the metallicity of 2D Ca-Cl crystals, unexpected piezoelectric effect, room-temperature ferromagnetism, as well as the distinct hydrogen storage and release capability of the Ca-Cl crystals in rGO membranes. Theoretical studies show that the formation of those abnormal crystals is attributed to the strong cation-pi interactions of the Ca2+ with the aromatic rings in the graphitic surfaces. Since strong cation-pi interactions also exist between other metal ions (such as Mg2+, Fe2+, Co2+, Cu2+, Cd2+, Cr2+ and Pb2+) and graphitic surfaces, similar 2D crystals with abnormal valence state of the metal cations and corresponding abnormal properties as well as novel applications are highly expected. Those findings further show the realistically potential applications of such abnormal CaCl material with unusual electronic properties in designing novel transistors and magnetic devices, hydrogen storage, catalyzer, high-performance conducting electrodes and sensors, with a size down to atomic scale.

physics.chem-ph↗

arXiv2018

Two-dimensional Ca-Cl crystals under ambient conditions observed directly by cryo-electron microscopy

Recently, we report the direct observation, under ambient conditions, of Na2Cl and Na3Cl as two-dimensional (2D) Na-Cl crystals, together with regular NaCl, on reduced graphene oxide membranes and on the surfaces of natural graphite powders from salt solutions far below the saturated concentration. However, what are these abnormal stoichiometries for high valence ions, such as calcium ions and copper ions still remain unknown. Here, using cryo-electron microscopy, we report the direct observation of two-dimensional (2D) Ca-Cl crystals on reduced graphene oxide (rGO) membranes, in which the calcium ions are only monovalent (i.e. +1). Remarkably, metallic properties rather than insulating are displayed by those CaCl crystals. We note that such CaCl crystals are obtained by simply incubating rGO membranes in salt solutions below the saturated concentration, under ambient conditions. Theoretical studies show that the formation of those abnormal crystals is attributed to the strong cation-pi interactions of the Ca2+ ions with the aromatic rings in the graphitic surfaces. Since strong cation-pi interactions also exist between other metal ions (such as Mg2+, Fe2+, Co2+, Cu2+, Cd2+, Cr2+ and Pb2+) and graphitic surfaces, similar 2D crystals with abnormal valence state of the metal cations and corresponding abnormal properties are highly expected. The 2D crystals with monovalent calcium ions show unusual electronic properties, and can be applicated in catalyzer, hydrogen storage, high-performance conducting electrodes and sensors. These findings also produce functionalized graphene including compact "graphene-metallic CaCl-insulating CaCl2" junction that can serve as transistors down to the atomic scale, and other devices for magnetic, optical and mechanical applications.

physics.chem-ph↗

arXiv2018

Unexpectedly high salt accumulation inside carbon nanotubes soaked in very dilute salt solutions

We experimentally demonstrate the formation of salt aggregations with unexpectedly high concentration inside multi-walled carbon nanotubes (CNTs) soaked only in dilute salt solutions and even in solutions containing only traces of salts. This finding suggests the blocking of fluid across CNTs by the salt aggregations when CNTs are soaked in a dilute salt solution with the concentration of seawater or even lower, which may open new avenues for the development of novel CNT-based desalination techniques. The high salt accumulation of CNTs also provides a new CNT-based strategy for the collection/extraction of noble metal salts in solutions containing traces of noble metal salts. Theoretical analyses reveal that this high salt accumulation inside CNTs can be mainly attributed to the strong hydrated cation-pi interactions of hydrated cations and pi electrons in the aromatic rings of CNTs.

cond-mat.mtrl-sci↗

arXiv2017

NaCl crystal from salt solution with far below saturated concentration under ambient condition

Under ambient conditions, we directly observed NaCl crystals experimentally in the rGO membranes soaked in the salt solution with concentration below and far below the saturated concentration. Moreover, in most probability, the NaCl crystals show stoichiometries behavior. We attribute this unexpected crystallization to the cation-π interactions between the ions and the aromatic rings of the rGO.

physics.chem-ph↗

arXiv2016

Highly Efficient Ion Rejection by Graphene Oxide Membranes via Ion-controlling Interlayer Spacing

Because they may provide ultrathin, high-flux, and energy-efficient membranes for precise ionic and molecular sieving in aqueous solution, GO membranes (partially oxidized, stacked sheets of graphene) have shown great potential in water desalination and purification, gas and ion separation, biosensors, proton conductors, lithium-based batteries and super-capacitors. Unlike carbon nanotube (CNT) membranes, in which the nanotube pores have fixed sizes, the pores of GO membranes - the interlayer spacing between GO sheets - are of variable size. This presents a challenge for using GO membranes for filtration. Despite the great efforts to tune and fix the interlayer spacing, it remains difficult both to reduce the interlayer spacing sufficiently to exclude small ions while keeping this separation constant against the tendency of GO membranes to swell when immersed in aqueous solution, which greatly affects the applications of GO membranes. Here, we demonstrate experimentally that highly efficient and selective ion rejection by GO membranes can be readily achieved by controlling the interlayer spacing of GO membranes using cations (K+, Na+, Ca2+, Li+ and Mg2+) themselves. The interspacing can be controlled with precision as small as 1 A, and GO membranes controlled by one kind of cation can exclude other cations with a larger hydrated volume, which can only be accommodated with a larger interlayer spacing. First-principles calculations reveal that the strong noncovalent cation-pi interactions between hydrated cations in solution and aromatic ring structures in GO are the cause of this unexpected behavior. These findings open up new avenues for using GO membranes for water desalination and purification, lithium-based batteries and super-capacitors, molecular sieves for separating ions or molecules, and many other applications.

cond-mat.mtrl-sci↗

arXiv2014

Molecular-Scale Hydrophilicity Induced by Solute: Molecular-thick Charged Pancakes of Aqueous Salt Solution on Hydrophobic Carbon-based Surfaces

We directly observed molecular-thick aqueous salt-solution pancakes on a hydrophobic graphite surface under ambient conditions employing atomic force microscopy. This observation indicates the unexpected molecular-scale hydrophilicity of the salt solution on graphite surfaces, which is different from the macroscopic wetting property of a droplet standing on the graphite surface. Interestingly, the pancakes spontaneously displayed strong positively charged behavior. Theoretical studies showed that the formation of such positively charged pancakes is attributed to cation-π interactions between Na+ ions in the aqueous solution and aromatic rings on the graphite surface, promoting the adsorption of water molecules together with cations onto the graphite surface; i.e., Na+ ions as a medium adsorbed to the graphite surface through cation-π interactions on one side while at the same time bonding to water molecules through hydration interaction on the other side at a molecular scale. These findings suggest that actual interactions regarding carbon-based graphitic surfaces including those of graphene, carbon nanotubes, and biochar may be significantly different from existing theory and they provide new insight into the control of surface wettability, interactions and related physical, chemical and biological processes.

cond-mat.soft↗