3D REDUCED GRAPHENE OXIDE/SIO 2 COMPOSITE FOR ICE NUCLEATION

Abstract

The present invention provides for an ice-nucleating particle for cloud seeding and other applications, which can initiate ice nucleation at a temperature of−8° C. Further, the ice nucleation particle number increased continuously and rapidly with the reducing of temperature. The ice nucleating particle in the present invention is a nanostructured porous composite of 3-dimensional reduced graphene oxide and silica dioxide nanoparticles (PrGO-SN). The present invention also provides for a process for synthesizing the PrGO-SN.

Claims

1. An ice nucleating composite for producing a plurality of ice crystals, wherein said composite initiates ice nucleation at a temperature of −8° C.; and wherein said composite multiplies the ice crystals in number when the temperature decreases at or below −8° C.

2. The ice nucleating composite as claimed in claim 1, wherein said composite is a porous nanostructured composite material of graphene metal oxide.

3. The ice nucleating composite of claim 1, wherein said composite is a porous composite of reduced graphene oxide (rGO) and silicon dioxide nanoparticles.

4. The ice nucleating composite of claim 1, wherein said composite is a three dimensional (3D) porous composite of reduced graphene oxide (rGO) and silicon dioxide nanoparticles.

5. The ice nucleating composite of claim 1, wherein the silicon dioxide nanoparticles are distributed uniformly across a hexagonal reduced graphene oxide (rGO) lattice micro-structure.

6. The ice nucleating composite of claim 1, wherein said composite exhibits a high water adsorption capacity of 118.86 cm.sup.3/g in low humidity conditions.

7. The ice nucleating composite of claim 1 wherein said composite has a high Brunauer-Emmett-Teller (BET) surface area.

8. The ice nucleating composite of claim 1, wherein said composite has a low water contact angle.

9. The ice nucleating composite of claim 1, wherein said composite comprises a plurality of pores of about 10-100 nm in size.

10. The ice nucleating composite of claim 1, wherein said composite has a high pore volume.

11. A process for preparing the ice nucleating composite as claimed in claim 1, the process comprising the steps of: preparing an aqueous dispersed graphene oxide solution; adding the aqueous solution of graphene oxide to ethanol, ammonium hydroxide and tetraethyl orthosilicate forming a homogenous mixture; sonicating the homogenous mixture to obtain a sonicated mixture; heating the sonicated mixture in an autoclave for hydrothermal synthesis thus obtaining the ice nucleating composite; rinsing the ice nucleating composite with a deionised water; and freeze -drying the composite to preserve the 3D micro-structure.

12. The process for preparing the ice nucleating composite as claimed in claim 11, wherein the concentration of graphene oxide solution was 2 mg/ml.

13. The process for preparing the ice nucleating composite as claimed in claim 11, wherein 20 ml of ethanol was added to the aqueous solution of graphene oxide.

14. The process for preparing the ice nucleating composite as claimed in claim 11, wherein 0.7 ml of ammonium hydroxide was added to the aqueous solution of graphene oxide.

15. The process for preparing the ice nucleating composite as claimed in claim 11, wherein 0.7 ml of tetraethyl orthosilicate was added to the aqueous solution of graphene oxide.

16. The process for preparing the ice nucleating composite as claimed in claim 11, wherein the homogenous mixture comprising the aqueous solution of graphene oxide, ethanol, ammonium hydroxide and tetraethyl orthosilicate is sonicated at room temperature for at least 30 minutes.

17. The process for preparing the ice nucleating composite as claimed in claim 11, wherein the sonicated mixture is heated in a Teflon lined, sealed autoclave.

18. The process for preparing the ice nucleating composite as claimed in claim 11, wherein the sonicated mixture is heated at 180° C. for at least 12 hours for hydrothermal synthesis.

19. The process for preparing the ice nucleating composite as claimed in claim 11, wherein the ice nucleating composite is washed with deionised water at least three times.

20. The process for preparing the ice nucleating composite as claimed in claim 11, wherein the ice nucleating composite is frozen in a freeze dryer at −100° C. for at least 24 hours.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0016] The subject matter that is regarded as the invention is particularly pointed out and distinctly claimed in the claims at the conclusion of the specification. The foregoing and other aspects, features, and advantages of the invention are apparent from the following detailed description taken in conjunction with the accompanying drawings in which—

[0017] FIG. 1A illustrates a schematic representation of the PrGO-SN composite porous structure that adsorbs and condenses water thereby triggering ice growth from the pores in accordance with an embodiment of the present invention;

[0018] FIG. 1B depicts the ice nucleation mechanism of the PrGO-SN composite in accordance with an embodiment of the present invention;

[0019] FIG. 2 illustrates a schematic flowchart for the synthesis of PrGO-SN in accordance with an embodiment of the present invention;

[0020] FIG. 3 graphically depicts a comparison of water vapor adsorption capacity of different PrGO-SN composites in accordance with an embodiment of the present invention;

[0021] FIG. 4A depicts the SEM image of the rGO sheet in accordance with an embodiment of the present invention;

[0022] FIG. 4B depicts the SEM image of the PrGO-SN composite where SiO2 nanoparticles were enveloped within the 3D rGO network in accordance with an embodiment of the present invention;

[0023] FIG. 4C depicts the SEM image of the PrGO-SN composite where SiO2 nanoparticles were enveloped within the 3D rGO network, when the scale bar is 200nm in accordance with an embodiment of the present invention;

[0024] FIG. 4D depicts the TEM image of the PrGO-SN composite in accordance with an embodiment of the present invention;

[0025] FIG. 4E depicts the structure of SiO2 nanoparticles in accordance with an embodiment of the present invention;

[0026] FIG. 4F depicts the FTIR spectra of rGO, SiO2 and the PrGO-SN composite, respectively in accordance with an embodiment of the present invention;

[0027] FIG. 5 graphically depicts the Simultaneous thermal analysis (STA) of the relative mass ratio of the PrGO-SN composite in accordance with an embodiment of the present invention;

[0028] FIG. 6A depicts the pore size distribution of PrGO-SN composite and rGO based on the Barrett-Joyner-Halenda method in accordance with an embodiment of the present invention;

[0029] FIG. 6B depicts the specific surface area (as,BET) of rGO and the PrGO-SN composite based on the Brunauer-Emmet-Teller method using N2 adsorption/desorption isotherm in accordance with an embodiment of the present invention;

[0030] FIG. 6C depicts a water vapor adsorption isotherm of rGO and the PrGO-SN at relative humidity ranging from 60% to 75% in accordance with an embodiment of the present invention;

[0031] FIG. 6D depicts the water contact angle measurement of the PrGO-SN composite and AgI particles, respectively in accordance with an embodiment of the present invention;

[0032] FIG. 7A depicts the ice nucleation activities of the PrGO-SN composite observed by E-SEM experiments under controlled temperature and water vapor pressure conditions in form of hexagonal ice crystals in accordance with an embodiment of the present invention;

[0033] FIG. 7B depicts the ice nucleation activities of the PrGO-SN composite observed by E-SEM experiments under controlled temperature and water vapor pressure conditions in form of bulk ice in accordance with an embodiment of the present invention;

[0034] FIG. 7C depicts the different ice formation patterns in the rough region with cavities in accordance with an embodiment of the present invention;

[0035] FIG. 7D depicts the different ice formation patterns in the smooth region in accordance with an embodiment of the present invention;

[0036] FIGS. 8A-8C shows additional E-SEM images of showed different ice formation patterns of of the PrGO-SN composite in rough region with cavities in accordance with an embodiment of the present invention; and

[0037] FIGS. 8D-8F shows additional E-SEM images of showed different ice formation patterns of of the PrGO-SN composite in the smooth region in accordance with an embodiment of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

[0038] The aspects of the ice nucleating particle of the present invention will be described in conjunction with FIGS. 1-8. In the Detailed Description, reference is made to the accompanying figures, which form a part hereof, and in which is shown by way of illustration specific embodiments in which the invention may be practiced. It is to be understood that other embodiments may be utilized and logical changes may be made without departing from the scope of the present invention. The following detailed description, therefore, is not to be taken in a limiting sense, and the scope of the present invention is defined by the appended claims.

[0039] The present invention introduces nanostructured composite materials for ice nucleation in cold cloud offering excellent in-plane and out-of-plane thermal conductivity which is in favor of ice nucleation of supercooled water. Further, the present invention provides for an ice nucleating particle which when presented in a cold atmospheric condition catalyze and enhance the formation and growth of ice crystals in mixed phase clouds. Furthermore, the present invention also provides for an ice nucleating particle, which can grow rapidly, and continuously with the constant reducing of temperature.

[0040] The present invention focusses at designing and synthesizing novel ice nucelating particles for ice nucleation in cold cloud. The invention introduces a porous composite of 3-dimensional (3D) reduced graphene oxide (rGO) and silica dioxide nanoparticles (PrGO-SN) aiming to initiate ice nucleation at higher temperature as well as sustained rapid ice crystal growth.

[0041] In an embodiment of the present invention, an interconnected 3D composite structure of PrGO-SN with narrow-sized SiO.sub.2 nanoparticles uniformly distributed across the entire rGO structure is produced via a single-step hydrothermal process. This composite promotes enhanced ice nucleation at relatively warm temperature with high ice nucleating activities based on the following hypothesis: 3D-rGO provided templates that facilitated ice crystal growth due to its hexagonal lattice structure; SiO.sub.2 nanoparticles enhanced the overall water molecule adsorption capabilities of the PrGO-SN composite and enabled less aggregation of the overall 3D-rGO structure, thus leading to more available sites for ice nucleation as illustrated in FIG. 1A and FIG. 1B.

[0042] FIG. 1A illustrates a schematic representation of the PrGO-SN composite porous structure that adsorbs and condenses water thereby triggering ice growth from the pores. FIG. 1B depicts the ice nucleation mechanism of the PrGO-SN composite.

[0043] Theoretical consideration of the enhanced ice formation mechanism:

[0044] Ice formation involves the processes of nucleation and growth. In the context of heterogeneous ice nucleation, water molecules start to form ice crystal seeds on the surface of INPs, and there are many factors that can influence the performance of ice nucleation. Numerous studies have been trying to analyze the rate of ice nucleation using various fundamental theories, one of which is classical nucleation theory (CNT), a simplified theoretical approach that describes that ice nucleation process. As Eq. 1 shows, the nucleation rate per unit volume J is mainly attributed to the properties of the INPs, including ρ.sub.1, the number density of sites for heterogeneous nucleation, Z.sub.j, the rate at which a nucleus overcomes the energy barrier and grows into a new phase (also known as Zeldovich factor which depends on Δφ* the formation energy of the critical cluster and N* the number of molecules in the cluster), and ΔF*, the free energy cost of creating the critical nucleus (ΔF* depends on θ the contact angle and ξ the geometry of the INPs). Other parameters present in Eq. 1 are k the Boltzmann constant and T the temperature.

[00001]$\begin{array}{cc}J={\rho }_I{Z}_j*\exp \left(-\frac{\Delta F^{*}}{kT}\right),Z_j=\sqrt{\frac{{\mathrm{\Delta \phi }}^{*}}{3\pi {\mathrm{kT}\left(N^{*}\right)}^2}},\Delta F^{*}=\Delta F_{HOMO}^{*}*f\left(\theta ,\xi \right)& \left(1\right)\end{array}$

[0045] Ice nucleation involves ordering of the water molecules that are rearranged into their favored lattice positions, such as the most common hexagonal ice crystals (I.sub.h) where water molecules arranged in layers of hexagonal rings. If the molecular geometry and chemistry of the INP surface is compatible with ice (such as lattice match), then an ice embryo formed on such surface within the liquid phase will have a lower free energy than an independent ice embryo and its growth will be facilitated. Therefore, an efficient nucleating surface would have low free energy of the interface which it forms with ice, which is consistent with Eq. 1 where smaller value of ΔF* leads to larger J.

[0046] The present invention aims to design and introduce a porous composite of 3-dimensional (3D) reduced graphene oxide (rGO) and silica dioxide nanoparticles (PrGO-SN) composite such that the surface of 3D-rGO serves as a template for ice crystal growth due to its hexagonal lattice structure (ΔF* lowering). Further, the presence of SiO.sub.2 nanoparticles in the PrGO-SN at the interlayer gaps between rGO sheets allows less aggregation of the overall 3D-rGO structure, thus leading to more available sites for ice nucleation (ρ.sub.1 increasing); more importantly, the hydrophilicity of SiO.sub.2 nanoparticles also facilitates the collection of water molecules on the rGO surface, which could facilitate sufficient water molecules for sustained rapid growth of ice crystals (θ lowering). In addition, it is reported that the minimum number of water molecules are necessary for ice nucleation to form a complete icosahedral symmetry of hexagonal geometry, thus more water molecules that are collected by the hydrophilic SiO.sub.2 nanoparticles can speed up the onset of ice nucleation and growth. Hence, both components of the PrGO-SN composite have a collective effect of enhancing the ice nucleation rate J.

[0047] Besides, the porous structure of the PrGO-SN composite of the present invention also enables liquid water condensation in these pores even below saturation by the inverse Kelvin effect. As Eq. 2 shows, the relative humidity with respect to water (RH.sub.w) for a pore to fill is predicted by the Kelvin effect with a negative sign to account for the concave nature of the meniscus:

[00002]$\begin{array}{cc}\ln \left(\frac{P_0}{P}\right)=-\frac{4\gamma \cos \left(\theta \right)V_l}{DRT}& \left(2\right)\end{array}$

[0048] Where

[00003]$\frac{P_0}{P}$

denotes the saturation ratio with respect to water, γ is the surface tension of water-vapor interface, V.sub.l is the molar volume of water, D is the pore diameter, 0 is the contact angle of water on the material, R is the gas constant and T is the temperature in Kelvin. Eq. 2 indicates that the narrower the pore width (smaller pore size), the lower the RH.sub.w required for pore condensation to occur. Conversely, the higher the contact angle of water on the material, the higher the RH.sub.w needed for pore filling. On top of the inverse Kelvin effect, the structure and composition of the PrGO-SN composite implied that the hydrophilicity of SiO.sub.2 nanoparticles can facilitate the collection of water molecules, and subsequently water molecules can reorganize in hexagonal structure on the rGO surface, which eventually leads to ice nucleation at suitable temperature.

[0049] On the other hand, since hydrogen bonds break and reform constantly depending on the thermal fluctuation of the water molecules, the balance between water-water and water-surface interactions is crucial for ice nucleation events, that is, if one type of interactions dominates the other, ice nucleation would not be favored because it would be either too volatile or too stable to trigger ice nucleation. Hence, surface properties are key to enabling and stabilizing ice nucleation. It is noteworthy that the balance between water-water and water-surface interactions is partly influenced by the quantity of water molecules around the PrGO-SN composite; if the quantity is high, then the water-water interaction will be stronger than the water-surface interaction, which would be difficult for water molecules to reorganize into hexagonal structure and form ice. This is supported by the study that the ice nucleation can be enhanced by a huge factor of 10 at the air-water interface than water-water interface. Since SiO.sub.2 nanoparticles can capture water vapor due to high water vapor adsorption capabilities and form a thin layer of liquid water on the PrGO-SN composite, there will exist a liquid/solid interface that has a positive bridging effect between water vapor and the solid surface of the composite. Ice nucleation will initiate from the thin water layer and the ice will grow at the expense of the water vapor in air.

[0050] Synthesis of the PrGO-SN composite:

[0051] The synthesis of PrGO-SN of the present invention is illustrated in FIG. 2. A single-step hydrothermal synthesis was carried out for the synthesis with following details. A GO aqueous dispersion was prepared using the improved Hummers method. 15 ml of GO solution (2 mg/ml concentration) as prepared above (using the Hummers method) was then mixed with 20 ml of ethanol (C.sub.2H.sub.60). Subsequently, 0.7 ml ammonium hydroxide solution (NH.sub.3.H.sub.2O) and 0.7 ml and 1.4 ml of Tetraethyl orthosilicate (TEOS) were added into the mixture respectively to prepare 2 separate samples. The mixtures are sonicated for 30 minutes then transferred into a sealed Teflon-lined autoclave and heated hydrothermally at 180° C. for 12 hours. Under sonication, silica nanoparticles were formed via St{umlaut over (0)}ber process, where TEOS was hydrolyzed in alcohol in the presence of NH.sub.3.H.sub.2O as a catalyst. The synthesized SiO.sub.2 nanoparticles became attached to the GO sheets in the dispersion by forming hydrogen bonds with oxygen-containing groups on GO sheets. The mixture then underwent self-assembly in a hydrothermal process to form a black-colored sponge-like structure of 3-dimensional reduced graphene oxide and silica dioxide nanoparticles (PrGO-SN). After hydrothermal process, formed PrGO-SN composite was washed with deionized water (DI) water three times. The washed PrGO-SN composite was then put into a freezer at −20° C. overnight and subsequently, the PrGO-SN composite was transferred into freeze dryer at −100° C. for 24 hours. The ice nucleation performance of the PrGO-SN composite was further determined through in-situ visual observation by Environmental-Scanning Electron Microscope (E-SEM).

[0052] Characterization and Measurements:

[0053] The synthesized PrGO-SN composite was characterized through Scanning Electron Microscopy (SEM, Quanta 250, FEI Company); Transmission Electron Microscopy (TEM, Tecnai from FEITM Company operating at 200 KV); A Fourier transform infrared Nicolet iS10 spectrometer (FTIR, Thermo Fisher Scientific, Inc.). Water static-contact-angle Measurements (Kyowa DM-701) elaborated with an interface Measurement & Analyses System and the droplets of 0.8 μl. The water vapor adsorption performance of the PrGO-SN composite was determined quantitatively via a water-vapor adsorption isotherm test (Brunauer-Emmett-Teller, Belsorb Max, Japan) in water-vapor mode. The samples were pretreated at 100° C. for 3 hours under a pressure <10.sup.−4 Pa before commencing the water vapor adsorption isotherm analysis and the whole test required 24 hours. Environmental scanning electron microscopy (E-SEM) was used for in-situ observation of the ice nucleation activities of the PrGO-SN composite. The water vapor adsorption isotherm analysis confirmed that PrGO-SN sample prepared by 0.7 ml of TEOS had higher water vapor adsorption capacity as shown in FIG. 3.

[0054] FIG. 3 illustrates a comparison of water vapor adsorption capacity of different PrGO-SN composites. It can be seen from the graph shown in FIG. 3 that at low relative humidity conditions ranging from 60% to 75%, the adsorbed water-vapor volume of the PrGO-SN (0.7 ml TEOS) sample was higher than that of the PrGO-SN(1.4 ml TEOS) sample; as the relative humidity increases, the difference in water vapor adsorption capacity was even larger.

[0055] The 3D-rGO/MO materials produced in this invention, when evaluated by micro-scale ice nucleation measurement, show that 3DrGO/SiO2 produced can initiate ice nucleation at −8° C. which is higher temperature than most previous reported materials such as AgI and feldspar. Further, the ice nucleation particle number increased continuously and rapidly with the reducing of temperature.

[0056] Surface morphology of rGO and the cross-sectional image of the PrGO-SN:

[0057] The microscopic surface morphology of rGO and the cross-sectional image of the PrGO-SN composite are shown in FIGS. 4A to 4E. When the GO dispersion underwent hydrothermal process as mentioned above, a well-connected 3D porous structure was formed with many interconnected rGO sheets as shown in FIG. 4A. As for the PrGO-SN composite, the SEM image confirmed that SiO2 nanoparticles were homogeneously embedded in rGO and distributed across almost the entire rGO network as shown in FIG. 4B. The internal structure of the PrGO-SN composite also revealed the overall distribution of SiO2 nanoparticles enveloped within the 3D-rGO network. Further observations under TEM suggested that SiO2 nanoparticles occupied the interlayer gaps between rGO sheets, indicating that the SiO2 nanoparticles played a spacer role in separating the rGO sheets and thus resulted in less aggregation compared to the pristine rGO. FIG. 4D shows different contrasts of rGO sheets and SiO2 nanoparticles, which indicated the co-existence of SiO2 nanoparticles and rGO layers. In addition, it can be found that SiO2 nanoparticles presented in spherical structure with an average size of 10-20 nm as shown in FIG. 4E.

[0058] Furthermore, Simultaneous Thermal Analysis (STA) was conducted to determine the composition of each component in the PrGO-SN composite, and the result indicated that the mass percentage of rGO in the PrGO-SN composite is about 18 wt % as shown in FIG. 5. FIG. 5, depicts the Simultaneous thermal analysis (STA) of the relative mass ratio of the PrGO-SN composite. It is indicated in FIG. 5 that rGO accounted for 18% of the total composite mass. Typically, the mass of composite did not change much until 500° C. Before 500° C., most of the mass loss was due to the evaporation of water molecules inside the composite; after 500° C., carbonaceous materials started to burn, resulting in significant mass loss.

[0059] The functional groups of each component of the PrGO-SN composite were confirmed by FTIR (Fourier transform infrared Nicolet iS10 spectrometer) as shown in FIG. 4F. Peaks of C=C, C—O and Si—O—Si from the composite sample confirmed the presence of both rGO and SiO2 nanoparticles. Moreover, the relatively strong peak of the composite at 1060-1075 cm-1 corresponds to the superimposition between the C—O and Si—O—Si peaks. The peaks of —OH and O—H were barely visible (FIG. 3F), implying that most of the oxygen-containing groups were removed during the hydrothermal reaction process. The slightly stronger -OH signal from the PrGO-SN composite than the rGO could result from the presence of silanol groups that normally associated with SiO2 nanoparticles.

[0060] The pore size distribution and total pore volume of both the PrGO-SN composite and rGO were determined by the Barrett-Joyner-Halenda (BJH) method. As FIG. 6A shows, BJH result demonstrated that the PrGO-SN composite had significantly more pores of size range between 10-100 nm and peaked at around 50 nm compared to rGO which had less pores of larger sizes, suggesting that the co-existence of SiO.sub.2 nanoparticles and 3D-GO framework contributed to the formation of smaller pores (10-100 nm) in the composite structure. In addition, the PrGO-SN composite has a total pore volume (V.sub.p) of 1.23 cm.sup.3/g, compared to that of rGO 0.69 cm.sup.3/g. This BJH result indicated that the porosity of the PrGO-SN composite has been greatly increased compared to the rGO. The specific surface area (a.sub.s,BET) of the rGO and the PrGO-SN composite were determined by the Brunauer-Emmet-Teller (BET) method using N.sub.2 adsorption/desorption isotherms with 167.31 m.sup.2/g for rGO and 178.84 m.sup.2/g for the composite, respectively as shown in FIG. 6B. The higher value of a.sub.s,BET of the composite was attributed to the less restacking of the flexible rGO sheets during the self-assembling process, where SiO.sub.2 nanoparticles functioned as spacers which separated the rGO sheets by occupying the interlayer gaps, caused less aggregation and therefore resulted in an increase in the surface area.

[0061] Water-vapor adsorption isotherm analysis was conducted to quantitatively determine the water-vapor adsorption capacity of the PrGO-SN composite compared to the rGO. It was found that, even at low relative humidity conditions ranging from 60% to 75%, the adsorbed water-vapor volume of the composite was higher than that of the rGO [118.86 cm.sup.3/g compared with that (105.95 cm.sup.3/g) of rGO at 75% R]), which enabled the composite to adsorb more water vapor that potentially contributed to ice nucleation at suitable temperature as shown in FIG. 6C. Although both PrGO-SN composite and rGO demonstrated good water vapor adsorption capacity, it can be inferred that the PrGO-SN composite could adsorb much more water vapor than the rGO at higher RH value. This feature was attributed to both the hydrophilicity of SiO.sub.2 nanoparticles and the porous structure of the PrGO-SN composite. Further, the water contact angle of the PrGO-SN composite was determined by deionized water static-contact-angle measurements. The PrGO-SN powder sample was pressed into a plate form through compression molding method, and the measured contact angle of the plate sample was used as approximation for the actual PrGO-SN composite particles. As shown in FIG. 6D, the contact angle of the PrGO-SN composite is as low as 36.2°, thereby confirming its strong hydrophilic property. A low contact angle can lead to higher ice nucleation activities because of the lowering of free energy cost of creating the critical nucleus thereby increasing the water vapor adsorption performance. In comparison, the contact angle of silver iodide (AgI) particles for example, is 131.1°, which shows strong hydrophobic property. Based on the above results and comparisons, PrGO-SN composite sample of the present invention has demonstrated the structure and property of a nanostructured porous materials with higher water vapor adsorption capacity, higher BET specific surface area and lower water contact angles (i.e. more hydrophilic). Such characteristics of PrGO-SN composite are in favor of initiating ice nucleation at an extremely lower critical temperature and vapor pressure in addition to rapid ice crystal growth.

[0062] Observation of ice nucleating on PrGO-SN composites:

[0063] Environmental scanning electron microscopy (E-SEM) was employed for in-situ observation of the ice nucleation activities of the PrGO-SN composite. For all E-SEM experiments, the supersaturated relative humidity conditions and the sub-zero temperature for the first occurrence of ice nucleation and the subsequent growth were controlled by adjusting the partial pressure of water vapor as well as the temperature in the chamber. Firstly, samples were pretreated in the chamber for 60 min with the temperature of the chamber set at −8° C. and the relative humidity (RH) at ˜80%. This pretreatment allows for stabilizing the temperature and relative humidity conditions. Secondly, RH in the chamber was gradually increased at a constant rate (˜5 Pa/s) until first ice nucleation events were observed, and the RH stopped increasing and was kept constant; meanwhile ice crystal growth progressed rapidly at this RH value. Multiple experiments were performed under such procedures and it was found that the RH value at which first nucleation event was observed ranged from 5% to 8% supersaturation. Same procedures were followed at even higher temperature of −7 and −6° C., but no ice nucleation events were observed regardless of the increase in RH. Therefore, −8 ° C. was determined as the highest and optimal ice nucleation temperature for the PrGO-SN composite. It is noteworthy that no water droplet was found at any stage throughout the E-SEM experiments, indicating that the water vapor was transformed directly into ice crystals.

[0064] E-SEM experiments showed that, under the same conditions, PrGO-SN composite-induced ice nucleation resulted in two different appearances of ice crystals: 1) those that tended to grow into individual hexagonal crystals; and 2) those merging with each other and forming bulk ice, as depicted in FIG. 7A and 7B respectively. This phenomenon suggested that different surface features of the PrGO-SN composite may have different influence on ice nucleation and growth. To further analyze such phenomenon, regions of the PrGO-SN composite with different morphologies were carefully observed by E-SEM observation: one with apparent topographic roughness such as large cavities on the surface, the other with relatively smooth surface absent of large cavities, as shown in FIG. 7C and FIG. 7D, respectively.

[0065] As shown in FIG. 7C, when RH reached ˜5% supersaturation, first ice nucleation event took place on the sample regions with large cavities and then started to grow within ˜10 s from the beginning of the experiment (c2). When RH increased to ˜8% supersaturation and ˜20 s into the experiment, ice crystals grew larger and displayed visible hexagonal shape in the cavity of the sample (c3). In comparison, FIG. 7D shows that ice nucleation was only observed on the sample regions with smooth surface until the conditions reached ˜8% supersaturation and ˜30 s from the beginning of the experiment (d2). However, in the later sample, once the ice crystals were formed, spontaneous ice growth occurred and ice crystals covered almost the entire surface of the sample within a short period of time (only ˜5 s) from the first ice nucleation event (d3). It is noteworthy that for both scenarios, the nucleated ice crystals can sustain their growth at constant RH.

[0066] Further, multiple E-SEM ice nucleation experiments were conducted, and more SEM images of ice nucleation events in rough region with cavities as shown in FIGS. 8A-8C; and relatively smooth region as shown in FIGS. 8D-8F respectively. As it can be seen from FIGS. 8A-8C, the E-SEM experiments showed different ice formation patterns in rough region with the presence of cavities. Alternatively, it can be seen from FIGS. 8D-8F the ice formation patterns in the smooth region is in form of hexagonal ice crystals and bulk ice.

[0067] It can be found that for the rough sample regions with large cavities, ice nucleation could be incepted on such large cavities and grown into hexagonal shape ice crystals (FIG. 7C). In the case of sample with relatively smooth regions, simultaneous ice nucleation occurred at multiple sites, and the formed ice crystals tended to merge and form large chunks of ice as can be seen from FIG. 7D The differences in ice crystal growth behaviors were affected by the regions with different surface roughness. In general, topographic roughness on the PrGO-SN composite tended to favor condensations of vapor into liquid. Specifically, in the case of porous composite of PrGO-SN, rough regions with larger surface areas possess cavities and more small pores than relatively smooth regions. As a result, condensed water vapor would be accumulated first in the cavities on the PrGO-SN composite, thus these locations would have higher ice nucleation activities due to the confined nucleation sites and sufficient water vapor uptake. On the other hand, relatively smooth PrGO-SN region tended to adsorb water vapor more homogeneously, thus ice nucleation tended to occur at multiple sites simultaneously; however, due to the competition of condensed water vapor among the neighboring sites, ice nucleation would take longer time to be observed visually. Once the ice nucleation event occurred at multiple sites, the formed small ice crystals would quickly merge together to form bulk ice). By observing the ice nucleating on PrGO-SN composites using the temperature/water-vapor-pressure controlled E-SEM, it was founded that the porous composite of PrGO-SN demonstrated the initiation of ice nucleation at higher temperature as well as continuous rapid ice crystal growth, which showed potential as a promising candidate for ice nucleation materials.

[0068] The 3DrGO/SiO2 produced in the present invention exhibit various advantages over standard ice nucleating materials. First advantage is the 3D reduced graphene oxide framework offers excellent in plane and out-of-plane thermal conductivity, which is in favor of ice nucleation of super cooled water. Second advantage is the highly porous and hydrophilic SiO2 nanoparticle contribute in adsorbing the free-moving water molecules and assisting in achieving the fixed and packed orientation of water molecules in order to form the ice. Both positive factors possessed by the 3D-rGO/SiO2 have not been achieved by standard ice nucleating particles.

[0069] The present invention aims at designing a nanostructured porous composite of 3-dimensional reduced graphene oxide and silica dioxide nanoparticles (PrGO-SN). An interconnected 3D composite structure of PrGO-SN with narrow-sized SiO.sub.2 nanoparticles uniformly distributed across the entire rGO structure was produced via controlled single-step hydrothermal process. The PrGO-SN composite not only offered hexagonal ice crystal growth via lattice match between the ice and crystalline structure of the substrate that may induce heterogeneous ice nucleation from its 3D rGO component, but also provided high Brunauer-Emmett-Teller (BET) surface area and water vapor adsorption capacity. In addition, PrGO-SN composite has good porosity and more hydrophilic surface from its SiO.sub.2 nanoparticles component which were all suitable factors to promote ice nucleation and growth. In-situ observations via an Environmental-Scanning Electron Microscope (E-SEM) confirmed the enhanced ice nucleation performance of the PrGO-SN composite evidenced by visible ice nucleation event starting from −8° C., 5-8% RH supersaturation. In addition, it was founded that ice nucleation was incepted on large cavities in the rougher region of the PrGO-SN composite sample and grew into hexagonal shape ice crystals. Alternatively, ice nucleation event occurred simultaneously at multiple sites in a smoother region of the sample, then merged rapidly together to form bulk ice. By observing the ice nucleating on PrGO-SN composites under E-SEM, it was confirmed that the porous composite of PrGO-SN demonstrated the initiation of ice nucleation at higher temperature as well as continuous rapid ice crystal growth.

[0070] Many changes, modifications, variations and other uses and applications of the subject invention will become apparent to those skilled in the art after considering this specification and the accompanying drawings, which disclose the preferred embodiments thereof. All such changes, modifications, variations and other uses and applications, which do not depart from the spirit and scope of the invention, are deemed to be covered by the invention, which is to be limited only by the claims, which follow.