Bi Nanocrystals Research Articles

Energy Band-Modulated SnO Anodes with Improved Rate Capacity and Initial Coulombic Efficiency for Sodium-Ion Batteries.

An efficient interface and composition modification strategy is proposed to significantly increase the rate capacity and initial Coulombic efficiency (ICE) of SnO anodes via energy band structure modulation for Na-ion batteries (SIBs). The as-fabricated SnO@Bi@C material with Bi nanocrystals homogeneously dispersed on and around the SnO surface is prepared by an electrospinning method. The excellently dispersed Bi nanocrystals realize an effective interface contact with SnO and Na2O, which effectively lowers the electron conduction barriers and promotes sodium-ion release and transport upon the desodiation process, increasing the rate capacity and ICE of the SnO anode. The prepared SnO@Bi@C exhibits a much higher rate capacity up to 10 A g-1, except an improved ICE of 80.67%, compared to 57.38% of SnO@C. Importantly, the intercalation of Na+ between layer-structured Bi galleries provides a good basis for excellent cycle stability due to the highways constructed inside the prepared composites. This finding provides an effective tactic to establish ion transport high-speed channels, which essentially increase the rate performance and the ICE of the SnO-based anodes.

Bismuth-constructed high-speed channeled for Bi/Sb2SnO5@PCFs composite as high-rate and long-life anode for sodium-ion batteries

To cope with the charging-time and driving-range issues of the power batteries, a composite and phase modification tactics is manifested to increase the cycling stability and rate capability of the Sb2SnO5 (SSO) anode for sodium-ion batteries (SIBs). The as-fabricated Bi/SSO@PCFs composite with Bi nanocrystals homogeneously dispersed on and around the SSO surface is prepared by an electrospinning method. The excellently dispersed Bi nanocrystals realize an effective contact with SSO, which effectively lowers the electron conduction barriers and promotes the sodium ion release as well as the transport upon the desodiation/sodiation process, increasing the rate capacity and cycle stability of the SSO anode. Importantly, a high-speed ion channel is constructed through the special layered Bi, and SbBi phase. The prepared Bi/SSO@PCFs anodes deliver a high rate capacity up to 25 A g−1 and long cycle life of 5000 cycles with 83 % capacity retention rate, sustaining an average capacity loss of 0.0034 % for each cycle. Particularly, the intercalation of Na+ between layer-structure Bi and SbBi galleries provides a good basis for excellent cycle performance due to small volume change and unobstructed ion channels. This finding provides an effective strategy to establish ion transport highways, which essentially increase the rate-capacity and cycle-life of the SSO-based anodes for SIBs.

Novel methodology to determine thermal properties of nanoparticles exclusively based on SAXS measurements applied to Bi nanocrystals and nanodroplets in a glass matrix

A novel methodology is presented to determine thermal properties of polydisperse nanocrystals and/or nanodroplets embedded in a homogeneous matrix using small-angle X-ray scattering (SAXS). It is based solely on SAXS measurements at multiple temperatures and multiple moduli of the scattering vector. The proposed methodology can quantify the linear coefficients of thermal expansion of confined spherical nanocrystals and/or nanodroplets and the radius dependence of the melting temperature of confined spherical nanocrystals, even in samples with a broad size distribution. It is described through its application on a nanocomposite consisting of Bi nanocrystals/nanodroplets embedded in a sodium borate glass matrix. The linear coefficient of thermal expansion of Bi nanocrystals in the glass was ca 50% higher than that of bulk crystalline Bi, and the coefficient of liquid Bi nanodroplets was 25% smaller than that of bulk liquid Bi. The melting temperature of the spherical Bi nanocrystals decreased by ca 130 K when particle radii decreased from 82 to 23 Å. Even though SAXS measurements are generally expected to provide low-resolution structural parameters, this demonstrates that this technique allows for the characterization of rather weak temperature-dependent variations of size parameters during in situ heating processes and across melting transitions.

Controllable Crystallization of Two-Dimensional Bi Nanocrystals with Morphology-Boosted CO2 Electroreduction in Wide pH Environments.

Two-dimensional low-melting-point (LMP) metal nanocrystals are attracting increasing attention with broad and irreplaceable applications due to their unique surface and topological structures. However, the chemical synthesis, especially the fine control over the nucleation (reduction) and growth (crystallization), of such LMP metal nanocrystals remains elusive as limited by the challenges of low standard redox potential, low melting point, poor crystalline symmetry, etc. Here, a controllable reduction-melting-crystallization (RMC) protocol to synthesize free-standing and surfactant-free bismuth nanocrystals with tunable dimensions, morphologies, and surface structures is presented. Especially, ultrathin bismuth nanosheets with flat or jagged surfaces/edges can be prepared with high selectivity. The jagged bismuth nanosheets, with abundant surface steps and defects, exhibit boosted electrocatalytic CO2 reduction performances in acidic, neutral, and alkaline aqueous solutions, achieving the maximum selectivity of near unity at the current density of 210mA cm-2 for formate evolution under ambient conditions. This work creates the RMC pathway for the synthesis of free-standing two-dimensional LMP metal nanomaterials and may find broader applicability in more interdisciplinary applications.

Surface Conductivity of Bi, Ga, In, and Sb Nanocrystals Condensed on Glassy Carbon Substrates

Surface Conductivity of Bi, Ga, In, and Sb Nanocrystals Condensed on Glassy Carbon Substrates

Electron flux at the Schottky junction of Bi NPs and WO3-supported g-C3N4: an efficient ternary S-scheme catalyst for removal of fluoroquinolone-type antibiotics from water.

Recently, global-scale attempts have been conducted to develop clean technologies and affordable materials to remediate pharmaceutical contaminants of water resources that are resistant to the biodegradation. In line with global efforts, this study reports a facile method to fabricate Bi nanocrystals in situ decorated on WO3 nanoplates and its composite with graphitic carbon nitride (WO3/Bi/g-C3N4) for photocatalytic degradation of fluoroquinolone-type antibiotics (ciprofloxacin and ofloxacin). The designed ternary S-scheme WO3/Bi/g-C3N4 composite material was fully characterized by physicochemical and electrochemical analysis. Depositing the cost-effective and earth-abundant Bi nanocrystals onto WO3 via a facile reduction route has been shown to increase the boosting of electron flux at their interface (Schottky junction). The S-scheme separation is confirmed by the calculation of band positions and the analysis of photogenerated hydroxyl radicals and holes. The complete removal of contaminants was obtained over the WO3/Bi/g-C3N4 photocatalyst after 90 min under visible light irradiation. The present work would provide a rational route for developing Bi NP-based photocatalysis to replace metallic Au, Pt, and Ag NPs.

Controlled Synthesis of Intermetallic Au2 Bi Nanocrystals and Au2 Bi/Bi Hetero-Nanocrystals with Promoted Electrocatalytic CO2 Reduction Properties.

The electrocatalytic properties of metal nanoparticles (NPs) strongly depend on their compositions and structures. Rational design of alloys and/or heterostructures provides additional approaches to modifying their surface geometric and electronic structures for optimized electrocatalytic performance. Here, a solution synthesis of freestanding intermetallic Au2 Bi NPs, the heterostructures of Au2 Bi/Bi hetero-NPs, and their promoted electrocatalytic CO2 reduction reaction (CO2 RR) performances were reported. It was revealed that the formation and in-situ conversion of heterogeneous seeds (e. g., Au) were of vital importance for the formation of intermetallic Au2 Bi and Au2 Bi/Bi hetero-NPs. It was also found that the Au components would act as the structure promoter moderating the binding strength for key intermediates on Bi surfaces. The alloying of Bi with Au and the formation of heterogeneous Au2 Bi/Bi interfaces would create more surface active sites with modulated electronic structures and stronger adsorption strengths for key intermediates, promoting the CO2 -to-HCOOH conversion with high activity and selectivity. This work presents a novel route for preparing intermetallic nanomaterials with modulated surface geometric/electric structures and promoting their electrocatalytic activities with alloying effects and interfacial effects. Such strategy may find wide application in catalyst design and synthesis for more electrocatalytic reactions.

Governing Interlayer Strain in Bismuth Nanocrystals for Efficient Ammonia Electrosynthesis from Nitrate Reduction

Electrochemical ammonia (NH3) synthesis from nitrate (NO3-) reduction offers an intriguing approach for both sustainable ammonia synthesis and environmental denitrification, yet it remains hindered by a complicated reaction pathway with various intermediates. Here we present that the interlayer strain compression in bismuth (Bi) nanocrystals can contribute to both activity and selectivity improvement toward NH3 electrosynthesis from NO3- reduction. By virtue of comprehensive spectroscopic studies and theoretical calculations, we untangle that the interlayer lattice compression shortens Bi-Bi bond to broaden the 6p bandwidth for electron delocalization, promoting the chemical affinities of nitrogen intermediates. Such a manipulation facilitates NO3- activation to reduce the energy barrier for activity improvement, and also alleviates *NO2 desorption to suppress nitrite generation. As a result, a strain-compressive Bi electrocatalyst yields a maximal Faradaic efficiency of 90.6% and high generation rate of 46.5 g h-1 gcat-1 with industrially scalable partial current density up to 300 mA cm-2 for NH3 product at the optimized conditions, respectively.

Phase-Dependent Electrocatalytic CO2 Reduction on Pd3 Bi Nanocrystals.

Alloying is a general strategy for modulating the electronic structures of catalyst materials. Compared to more common solid-solution alloys, intermetallic alloys feature well-defined atomic arrangements and provide the unique platform for studying the structure-performance correlations. It is, unfortunately, synthetically challenging to prepare the nanostructures of intermetallic alloys for catalysis research. In this contribution, we prepare intermetallic Pd3 Bi nanocrystals of a uniform size via a facile solvothermal method. These nanocrystals can phase-transform into solid solution alloy via thermal annealing while retaining a similar composition and size. In 0.1 M KHCO3 aqueous solution, the intermetallic Pd3 Bi can selectively reduce CO2 to formate with high selectivity (≈100 %) and stability even at <-0.35 V versus reversible hydrogen electrode, whereas the solid solution alloy has limited formate selectivity of <60 %. Such unique phase-dependence is understood via theoretical simulations showing that the crystallographic ordering of Pd and Bi atoms within intermetallic alloys can suppress CO poisoning and enhance the *OCHO adsorption during electrochemical CO2 reduction to formate.

Optical control of heater based on Cu2−xSe:Bi nano-crystals

A strategy of accurate optical control of the heater is firstly put forward based on the photothermal conversion of Cu2−xSe:Bi nanoparticles film. The Cu2−xSe nanoparticles doped with low concentration Bi are prepared by microwave-assisted technology. The differential spectrum of photothermal conversion is used to evaluate the photothermal conversion of different processes and the mechanism is analyzed in detail. The photothermal conversion of the Cu2−xSe:Bi nanoparticle thin film can mainly be ascribed to the localized surface plasmon resonances (LSPR) characteristic due to the high carrier concentration. The process of the photothermal conversion is clearly divided into three stages corresponding to the different heat exchange ways The temperature can be tuned precisely by changing laser power at the 0.01-watt magnitude, simultaneously obey the law of linear change rule and perform good repeatability. This work may offer a new strategy in the development of non-contact micro area precise temperature control technology.

Determination of the melting temperature of spherical nanoparticles in dilute solution as a function of their radius by exclusively using the small-angle X-ray scattering technique

In this investigation the dependence on radius of the melting temperature of dilute sets of spherical nanocrystals with wide radius distributions was determined by a novel procedure exclusively using the results of small-angle X-ray scattering (SAXS) measurements. This procedure is based on the sensitivity of the SAXS function to small and rather sharp variations in the size and electron density of nanocrystals at their melting temperature. The input for this procedure is a set of experimental SAXS intensity functions at selected q values for varying sample temperatures. In practice, the sample is heated from a minimum temperature, lower than the melting temperature of the smallest nanocrystals, up to a temperature higher than the melting temperature of the largest nanocrystals. The SAXS intensity is recorded in situ at different temperatures during the heating process. This novel procedure was applied to three samples composed of dilute sets of spherical Bi nanocrystals with wide radius distributions embedded in a sodium borate glass. The function relating the melting temperature of Bi nanocrystals with their radius – determined by using the procedure proposed here – agrees very well with the results reported in previous experimental studies using different methods. The results reported here also evidence the predicted size-dependent contraction of Bi nanocrystals induced by the large surface-to-volume ratio of small nanocrystals and an additional size-independent compressive stress caused by the solid glass matrix in which liquid Bi nanodroplets are initially formed. This last effect is a consequence of the increase in the volume of Bi nanoparticles upon crystallization and also of differences in the thermal expansion coefficients of the crystalline phase of Bi and the glass matrix. This additional stress leads to a depression of about 10 K in the melting temperature of the Bi nanocrystals confined in the glass. The procedure described here also allowed the determination of the specific masses and thermal expansion coefficients of Bi nanoparticles in both liquid and crystalline phases.

Crystalline Sb or Bi in amorphous Ti-based oxides as anode materials for sodium storage

A simple synthesis has been developed for watermelon-like nanocomposites with Ti-based oxides as the matrix. Using the case of Sb nanocrystals in amorphous TiPOx as an example, in-situ/ex-situ techniques, first-principle calculations and control experiments confirm that the formation of Ti-based oxides promotes the reduction of Sb3+ to Sb by NH3 at an elevated temperature. A similar synthesis process also succeeds for Sb nanocrystals in amorphous TiO2 and for Bi nanocrystals in amorphous TiPOx, confirming the promising potential of this synthesis. More importantly, the nanocomposite composed by crystalline Sb in an amorphous TiPOx matrix, as the anode material for sodium storage, concurrently exhibits a long cycle life (~1000 cycles) and a high capacity retention (~82%), suggesting the advantages of watermelon-like structures.

Bismuth embedded silica nanoparticles loaded with autophagy suppressant to promote photothermal therapy

An unpredicted side effect of photothermal therapy (PTT) is agitated by hyperthermia which results in damage to healthy tissue. Developing PTT platforms, enabling effective tumor ablation under mild irradiation conditions, is of wide interest, but challenging. Here, we investigated bismuth crystals embedded silica (Bi@SiO2) nanoparticles, loaded with an autophagy inhibitor (chloroquine, CQ). It was found that SiO2 effectively prevented the oxidization of Bi nanocrystals in the physiological environment and could serve as a scatter layer to improve NIR absorption, enabling a high photothermal conversion efficiency (~43%) and excellent photostability. Furthermore, the findings indicated that CQ molecules, delivered intracellularly by the particles, significantly weakened the degradation of autolysosomes by lysosome within the tumor cells, thus inducing suppression effect to autophagy and resistance to photothermia. Both in vitro and in vivo anti-tumor effects were consequently promoted owing to the combined effects enabled by Bi@SiO2-CQ nanoparticles under mild NIR irradiation conditions. This study demonstrates a potential new PTT platform with superior therapeutic efficacy.

Surface molecular kinetics on the outermost layer characterized by nucleation of Mg-vapor atoms

The state of organic surfaces/interfaces greatly affects the performance of organic electronic devices. Various methods have been reported to investigate the surface glass transition temperature, which is based on the dynamics of molecules or polymer chains existing at the depth of several to several-tens nanometers from surface. However, no report has published about the characterization of molecular kinetics on the outermost surface. We report that the surface nucleation of Mg-vapor atoms reflects the molecular kinetics on the outermost surface. The nucleation rate of vaporized atoms/molecules is generally accelerated on steps existed on crystalline surface, to the contrary we found suppressed nucleation of Mg nanocrystals around the steps on a diarylethene crystalline surface during Mg-vapor deposition. On the other hand, Pb, Bi, and Te nanocrystals tended to accumulate the steps. The difference between acceleration and suppression of metal nucleation on the steps was attributed to molecular kinetics on the outermost surface and intensity of van der Waals interaction between metal atoms and the molecules. Mg having the weak interaction with organic molecules is suitable for characterizing molecular kinetics on the outermost surface. The observation of Mg nucleation can play a role in measuring molecular kinetics on the outermost surfaces. The state of organic surfaces/interfaces greatly affects the performance of organic electronic devices. Various methods have been reported to investigate the surface glass transition temperature, which is based on the dynamics of molecules or polymer chains existing at the depth of several to several-tens nanometers from surface. However, no report has published about the characterization of molecular kinetics on the outermost surface. We report that the surface nucleation of Mg-vapor atoms reflects the molecular kinetics on the outermost surface. The nucleation rate of vaporized atoms/molecules is generally accelerated on steps existed on crystalline surface, to the contrary we found suppressed nucleation of Mg nanocrystals around the steps on a diarylethene crystalline surface during Mg-vapor deposition. On the other hand, Pb, Bi, and Te nanocrystals tended to accumulate the steps. The difference between acceleration and suppression of metal nucleation on the steps was attributed to molecular kinetics on the outermost surface and intensity of van der Waals interaction between metal atoms and the molecules. Mg having the weak interaction with organic molecules is suitable for characterizing molecular kinetics on the outermost surface. The observation of Mg nucleation can play a role in measuring molecular kinetics on the outermost surfaces. • The surface nucleation of Mg-vapor atoms reflects the molecular kinetics on the outermost surface. • We found suppressed nucleation of Mg nanocrystals around the steps on a diarylethene crystalline surface. • The suppressed nucleation was attributed to surface molecular kinetics and weak van der Waals interaction.

Colloidal Bismuth Nanocrystals as a Model Anode Material for Rechargeable Mg-Ion Batteries: Atomistic and Mesoscale Insights.

At present, the technical progress of secondary batteries employing metallic magnesium as the anode material has been severely hindered due to the low oxidation stability of state-of-the-art Mg electrolytes, which cannot be used to explore high-voltage (>3 V versus Mg2+/Mg) cathode materials. All known electrolytes based on oxidatively stable solvents and salts, such as Mg(ClO4)2 and Mg bis(trifluoromethanesulfonimide), react with the metallic magnesium anode, forming a passivating layer at its surface and preventing the reversible plating and stripping of Mg. Therefore, in a near-term effort to extend the upper voltage limit in the exploration of future candidate Mg-ion battery cathode materials, bismuth anodes have attracted considerable attention due to their efficient magnesiation and demagnesiation alloying reaction in such electrolytes. In this context, we present colloidal Bi nanocrystals (NCs) as a model anode material for the exploration of cathode materials for rechargeable Mg-ion batteries. Bi NCs demonstrate a stable capacity of 325 mAh g-1 over at least 150 cycles at a current density of 770 mA g-1, which is among the most-stable performance of Mg-ion battery anode materials. First-principles crystal structure prediction methodologies and ex situ X-ray diffraction measurements reveal that the magnesiation of Bi NCs leads to the simultaneous formation of the low-temperature trigonal structure, α-Mg3Bi2, and the high-temperature cubic structure, β-Mg3Bi2, which sheds insight into the high stability of this reversible alloying reaction. Furthermore, small-angle X-ray scattering measurements indicate that although the monodispersed, crystalline nature of the Bi NCs is indeed disturbed during the first discharge step, no notable morphological or structural changes occur in the following electrochemical cycles. The cost-effective and facile synthesis of colloidal Bi NCs and their remarkably high electrochemical stability upon magnesiation make them an excellent model anode material with which to accelerate progress in the field of Mg-ion secondary batteries.

A Shape-Induced Orientation Phase within 3D Nanocrystal Solids.

When nanocrystals self assemble into ordered superstructures they form functional solids that may inherit the electronical properties of the single nanocrystals. To what extent these properties are enhanced depends on the positional and orientational order of the nanocrystals within the superstructure. Here, the formation of micrometer-sized free-standing supercrystals of faceted 20 nm Bi nanocrystals is investigated. The self-assembly process, induced by nonsolvent into solvent diffusion, is probed in situ by synchrotron X-ray scattering. The diffusion-gradient is identified as the critical parameter for controlling the supercrystal-structure as well as the alignment of the supercrystals with respect to the substrate. Monte Carlo simulations confirm the positional order of the nanocrystals within these superstructures and reveal a unique orientation phase: the nanocrystal shape, determined by the atomic Bi crystal structure, induces a total of 6 global orientations based on facet-to-facet alignment. This parallel alignment of facets is a prerequisite for optimized electronic and optical properties within designed nanocrystal solids.

In Situ Atomic-Scale Study of Particle-Mediated Nucleation and Growth in Amorphous Bismuth to Nanocrystal Phase Transformation.

Understanding classical and nonclassical mechanisms of crystal nucleation and growth at the atomic scale is of great interest to scientists in many disciplines. However, fulfilling direct atomic‐scale observation still poses a significant challenge. Here, by taking a thin amorphous bismuth (Bi) metal nanosheet as a model system, direct atomic resolution of the crystal nucleation and growth initiated from an amorphous state of Bi metal under electron beam inside an aberration‐corrected transmission electron microscope is provided. It is shown that the crystal nucleation and growth in the phase transformation of Bi metal from amorphous to crystalline structure takes place via the particle‐mediated nonclassical mechanism instead of the classical atom‐mediated mechanism. The dimension of the smaller particles in two contacted nanoparticles and their mutual orientation relationship are critical to governing several coalescence pathways: total rearrangement pathway, grain boundary migration‐dominated pathway, and surface migration‐dominated pathway. Sequential strain analyses imply that migration of the grain boundary is driven by the strain difference in two Bi nanocrystals and the coalescence of nanocrystals is a defect reduction process. The findings may provide useful information to clarify the nanocrystal growth mechanisms of other materials on the atomic scale.

Thiol-capped Bi nanoparticles as stable and all-in-one type theranostic nanoagents for tumor imaging and thermoradiotherapy

Bismuth (Bi)-based semiconductors and composites have been well developed for cancer treatments due to their multimodal diagnostic and therapeutic functions, while the development of metallic Bi nanocrystals is rather hindered by the easy-oxidation and unsatisfactory near-infrared photoabsorption. Herein, we prepared uniform Bi nanoparticles (∼40 nm) capped with thiol ligands (Bi-SR) through the chemical reduction method and then surface-modified them with PEGylated phospholipids. The resulting Bi-SR-PEG has strong NIR absorbance and high photothermal conversion efficiency of 45.3%. Importantly, thiol ligands on the surface of Bi-SR-PEG can significantly prevent the metal Bi core from oxidation because of the strong chemisorption energy between sulfur and metal, thus maintaining the high stability and long-term near-infrared photoabsorption. More importantly, given the low toxicity, good blood compatibility and high X-ray attenuation coefficient, Bi-SR-PEG can passively accumulatein the tumor area through intravenous injection, endowing them with the simultaneous tumor CT imaging and thermoradiotherapy, and thereafter they can be metabolized and excreted from the mice body overtime. Therefore, the satisfying therapeutic effect of tumors can be achieved, undoubtedly verifying that Bi-SR-PEG can be used as a novel, stable and all-in-one type theranostic nanoagent for cancer treatment.

Size- and shape-dependent surface thermodynamic properties of nanocrystals

As the fundamental properties, the surface thermodynamic properties of nanocrystals play a key role in the physical and chemical changes. However, it remains ambiguous about the quantitative influence regularities of size and shape on the surface thermodynamic properties of nanocrystals. Thus by introducing interface variables into the Gibbs energy and combining Young-Laplace equation, relations between the surface thermodynamic properties (surface Gibbs energy, surface enthalpy, surface entropy, surface energy and surface heat capacity), respectively, and size of nanocrystals with different shapes were derived. Theoretical estimations of the orders of the surface thermodynamic properties of nanocrystals agree with available experimental values. Calculated results of the surface thermodynamic properties of Au, Bi and Al nanocrystals suggest that when r > 10 nm, the surface thermodynamic properties linearly vary with the reciprocal of particle size, and when r < 10 nm, the effect of particle size on the surface thermodynamic properties becomes greater and deviates from linear variation. For nanocrystals with identical equivalent diameter, the more the shape deviates from sphere, the larger the surface thermodynamic properties (absolute value) are.

Melting and freezing temperatures of confined Bi nanoparticles over a wide size range

The size dependences of the melting and freezing temperatures, T m and T f, respectively, of spherical Bi nanoparticles embedded in a sodium borate glass were determined by applying a new experimental procedure based on the combined and simultaneous use of small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS). This experimental procedure is particularly useful for materials in which a widely polydisperse set of nanoparticles are embedded. The results provide additional and stronger evidence supporting the main previous conclusions: (i) the melting and freezing temperatures both decrease linearly for increasing reciprocal radius (1/R); and (ii) the effect of undercooling is suppressed for Bi nanoparticles with radii smaller than a critical value equal to 1.8 nm. These results confirm a previously proposed low-resolution structural model for Bi nanocrystals below their melting temperature and with radius R &gt; 1.8 nm, which consists of a crystalline core surrounded by a disordered shell. In the present work, a number of samples with different and partially overlapping radius distributions were studied, allowing the determination of T m(R) and T f(R) functions over a wide range of radii (1 &lt; R &lt; 11 nm). Comparison of the experimentally determined T m(R) and T f(R) functions corresponding to different samples indicates good reproducibility of the experimental results. This allowed the verification of the robustness of the experimental procedure based on in situ combined use of SAXS and WAXS for determination of the radius dependence of the melting and freezing temperatures of spherical nanoparticles in dilute solution.