SearcharxivSearch

arXiv subjects

Haiping Fang

Publications and source records attributed to Haiping Fang.

At least 19 recordsLinked to original sources

Stability Mechanisms of Unconventional Stoichiometric Crystals Exampled by Two-Dimensional Na2Cl on Graphene under Ambient Conditions

Compounds harboring active valence electrons, such as unconventional stoichiometric compounds of main group elements including sodium, chlorine, and carbon, have conventionally been perceived as unstable under ambient conditions, requiring extreme conditions including extra-high pressure environments for stability. Recent discoveries challenge this notion, showcasing the ambient stability of two-dimensional Na2Cl and other unconventional stoichiometric compounds on reduced graphene oxide (rGO) membranes. Focusing on the Na2Cl crystal as a case study, we reveal a mechanism wherein electron delocalization on the aromatic rings of graphene effectively mitigates the reactivity of Na2Cl, notably countering oxygen-induced oxidation--a phenomenon termed the Surface Delocalization-Induced Electron Trap (SDIET) mechanism. Theoretical calculations also show a substantial activation energy barrier emerges, impeding oxygen infiltration into and reaction with Na2Cl. The remarkable stability was further demonstrated by the experiment that Na2Cl crystals on rGO membranes remain almost intact even after prolonged exposure to a pure oxygen atmosphere for 9 days. The discovered SDIET mechanism presents a significant leap in stabilizing chemically active substances harboring active valence electrons under ambient conditions. Its implications transcend unconventional stoichiometric compounds, encompassing main group and transition element compounds, potentially influencing various scientific disciplines.

physics.chem-ph

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

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

Ray Theory of Waves

Accurate and efficient prediction of three-dimensional (3D) fields in wave interactions with large, complex-shaped objects is essential for applications in electromagnetic computation, computer graphics, optical metrology, and freeform optics. However, existing methods face significant challenges: numerical techniques are computationally intensive and impractical for large objects, while ray tracing neglects wave properties and remains inefficient, relying solely on ray bundles. In this Letter, we present the Ray Theory of Waves (RTW), which introduces wavefront curvature (WFC) as an intrinsic property of a ray to describe wave divergence and convergence. Using differential geometry, we derive the wavefront equation, rigorously relating WFC of incident, reflected, and refracted waves, enabling accurate calculation of field amplitude and phase along a ray. To address diffraction effects at singularities and compute the total field, we propose an anti-conventional strategy. The flexibility, precision and performance of RTW are demonstrated through the calculation of 3D scattering pattern of an ellipsoidal drop. Importantly, the method clarifies several longstanding queries about Airy theory since the 19th century. RTW constitutes a theoretical breakthrough, opening new avenues for practical applications.

physics.optics

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

Ultrasensitive piezoelectric sensor based on two-dimensional Na2Cl crystals with periodic atom vacancies

Pursuing ultrasensitivity of pressure sensors has been a long-standing goal. Here, we report a piezoelectric sensor that exhibits supreme pressure-sensing performance, including a peak sensitivity up to 3.5*10^6 kPa^-1 in the pressure range of 1-100 mPa and a detection limit of less than 1 mPa, superior to the current state-of-the-art pressure sensors. These properties are attributed to the high percentage of periodic atom vacancies in the two-dimensional Na2Cl crystals formed within multilayered graphene oxide membrane in the sensor, which provides giant polarization with high stability. The sensor can even clearly detect the airflow fluctuations surrounding a flapping butterfly, which have long been the elusive tiny signals in the famous "butterfly effect". The finding represents a step towards next-generation pressure sensors for various precision applications.

physics.app-ph

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

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

Super strong paramagnetism of aromatic peptides adsorbed with monovalent cations

We experimentally demonstrated that the AYFFF self-assemblies adsorbed with various monovalent cations (Na+, K+, and Li+) show unexpectedly super strong paramagnetism. The key to the super strong paramagnetism lies in the hydrated cation-π interactions between the monovalent cations and the aromatic rings in the AYFFF assemblies, which endows the AYFFF-cations complex with magnetic moments.

physics.bio-ph

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

Unexpectedly super strong paramagnetism of aromatic peptides due to cations

We found that the AYFFF self-assemblies in the chloride solution of some divalent cations ($Zn^{2+}, Mg^{2+},$ and $Cu^{2+}$) display super strong paramagnetism, which may approach the mass susceptibility of ferromagnetism. We attribute the observed super strong paramagnetism to the existence of the aromatic rings, which interact with the cations through cation-π interaction.

physics.bio-ph

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

Unexpectedly strong diamagnetism and superparamagnetism of aromatic peptides due to self-assembling and cations

There is a considerable amount of work that shows the biomagnetism of organic components without ferromagnetic components at the molecular level, but it is of great challenge to cover the giant gap of biomagnetism between their experimental and theoretical results. Here, we show that the diamagnetism of an aromatic peptide, the AYFFF, is greatly enhanced for about 11 times by self-assembling, reaching two orders of magnitude higher than the mass susceptibility of pure water. Moreover, the AYFFF self-assemblies further mixed with ZnCl2 solution of sufficiently high concentrations display superparamagnetism, with the mass susceptibility reaching more than two orders of magnitude higher than the absolute value of pure water, which may approach the mass susceptibility of ferromagnetism. The aromatic rings in the peptide molecules and the cations are the keys to such a strong diamagnetism and superparamagnetism of aromatic peptides.

physics.bio-ph

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

Enhanced contact angle hysteresis of salt aqueous solution on graphite surface by a tiny amount of cation

We experimentally observed the enhanced contact angle hysteresis (CAH) of dilute aqueous salt solution on graphite surface, i.e., 40.6$^\circ$, 34.6$^\circ$, and 27.8$^\circ$, for LiCl, NaCl, and KCl, indicating the effective tuning of the CAHs by cations. Molecular dynamics simulations reveal that the preferential adsorption of cations on the HOPG surface due to the cation-π interaction pins the water at the backward liquid-gas-solid interfaces, reducing the receding contact angle and hence enhancing the CAH. This finding provides a simple method to control the contact angle and the CAH of aqueous drops on graphitic surfaces such as graphene, carbon nanotube, biomolecules, and airborne pollutants.

physics.app-ph

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

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

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