Method of fabricating a photocatalyst for water splitting

Abstract

The method of fabricating a photocatalyst for water splitting includes electrospinning a Zn-based solution mixed with CdS nanoparticles and then calcining to produce CdS nanoparticle decorated ZnO nanofibers having significant photocatalytic activity for water splitting reactions. The photocatalyst fabricated according to the method can produce H.sub.2 at a rate of 820 molh.sup.1g.sup.1 catalyst from aqueous solution under light irradiation.

Claims

1. A method of fabricating a photocatalyst for water splitting, comprising the steps of: providing a first semiconductor in nanoparticle form; mixing a first solution including an organic solvent with a second solution including an organic solvent to provide an electrospinning sol-gel, the first solution including a polymer and the second solution including a zinc salt; adding the first semiconductor in nanoparticle form to the electrospinning sol-gel to provide a colloidal solution; stirring the colloidal solution for a first period of time; electrospinning the colloidal solution after the first period of time to provide an electrospun nanofiber mat; drying the nanofiber mat under vacuum for a second period of time; and calcinating the nanofiber mat to provide the photocatalyst for water splitting, wherein the photocatalyst for water splitting includes nanofibers of a second semiconductor doped with the nanoparticles of the first semiconductor, the first semiconductor including a narrow band gap semiconductor selected from the group consisting of ZnS, CdS, CuO, CuS, and In.sub.2O.sub.3, the second semiconductor including zinc oxide.

2. The method of claim 1, wherein the organic solvent is dimethylformamide.

3. The method of claim 1, wherein the polymer solution comprises poly(-caprolactone).

4. A method for hydrogen production using water splitting, comprising the steps of: adding the photocatalyst of claim 1 to an aqueous solution, the aqueous solution including Na.sub.2SO.sub.3 and Na.sub.2S ions; irradiating the aqueous solution with solar light to produce hydrogen.

5. The method according to claim 4, wherein the step of irradiating is carried out at room temperature.

6. A method of fabricating a photocatalyst for water splitting, comprising the steps of: producing cadmium sulfide nanoparticles; mixing a polymer solution with a solution including a zinc salt to form an electrospinning sol-gel; adding the cadmium sulfide nanoparticles to the electrospinning sol-gel to provide a colloidal solution; stirring the colloidal solution for a first period of time; electrospinning the colloidal solution after the first period of time to provide an electrospun nanofiber mat; drying the nanofiber mat under vacuum for a second period of time; and calcinating the nanofiber mat to provide the photocatalyst for water splitting, the photocatalyst for water splitting comprising zinc oxide nanofibers doped with cadmium sulphide nanoparticles.

7. The method according to claim 6, further comprising: forming the cadmium sulphide nanoparticles by combining cadmium acetate with an ammonium sulfide solution under vigorous stirring.

8. The method according to claim 6, wherein the first period of time is about 5 hours and the second period of time is about 24 hours.

9. The method according to claim 8, wherein the calcinating comprises calcinating in Ar atmosphere at about 200 C. for about 30 minutes.

10. The method according to claim 6, wherein the polymer solution comprises poly(-caprolactone) and an organic solvent.

11. The method according to claim 10, wherein the organic solvent is dimethylformamide (DMF).

12. A photocatalyst produced according to the method of claim 6.

13. A method for hydrogen production using water splitting, comprising the steps of: adding the photocatalyst of claim 12 to an aqueous solution, the aqueous solution including Na.sub.2SO.sub.3 and Na.sub.2S ions; irradiating the aqueous solution with light to produce hydrogen.

14. The method according to claim 13, wherein the step of irradiating is carried out at room temperature.

15. The method according to claim 13, wherein about 50 mg of the photocatalyst is added to about 50 mL of the aqueous solution.

16. The method according to claim 13, further comprising sonicating the aqueous solution after adding the photocatalyst.

17. The method according to claim 13, wherein the light is solar light.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIGS. 1A-1B show field effect scanning electron microscope (FESEM) images of the CdS NP-doped ZnO NFs before calcination; FIGS. 1C-1D show scanning electron microscope (SEM) images of CdS NP-doped ZnO NFs after calcination at 200 C. for 30 min.

(2) FIG. 2 shows energy-dispersive X-ray (EDX) analysis of the CdS NP-doped ZnO NFs after calcination at 200 C. for 30 min.

(3) FIG. 3 shows X-ray diffraction (XRD) patterns of CdS NPs, ZnO NFs, and CdS NP-doped ZnO NFs after calcination.

(4) FIGS. 4A-4D show transmission electrode microscopy (TEM) images of the calcined Cds NP-doped ZnO NFs; FIG. 4A shows a TEM image for a single Cds NP-doped ZnO NF; FIG. 4B shows an HR-TEM image of the marked area in FIG. 4A; FIG. 4C shows a scanning transmission electrode microscopy (STEM) image of one nanofiber with STEM-EDX linescan; FIG. 41) shows TEM-EDX line analysis for the line in FIG. 4C; FIG. 4E shows the TEM-EDX spectrum of the nanofibers.

(5) FIG. 5 is a graph showing the amounts of H.sub.2 gas photocatalytically evolved from an aqueous solution containing Na.sub.2SO.sub.3 and Na.sub.2S in the presence of the CdS NPs-doped ZnO NFs, ZnO NFs, and CdS NPs.

(6) FIG. 6 is a graph showing the reproducibility of photocatalytic H.sub.2 gas evolution in the presence of the CdS NPs-doped ZnO NFs.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

(7) A method of fabricating a photocatalyst for water splitting provided herein includes providing a first semiconductor in nanoparticle form; mixing a polymer solution with a solution including an organic solvent and a salt of Zn, Ti or Sn, to provide an electrospinning sol-gel; adding the first semiconductor in nanoparticle form to the electrospinning sol-gel to provide a colloidal solution; stirring the colloidal solution for a first period of time; electrospinning the colloidal solution after the first period of time to provide electrospun nanofiber (NF) mats; drying the NF mats under vacuum for a second period of time; and calcinating the NF mats to provide the photocatalyst for water splitting (also referred to as composite NFs, herein). The photocatalyst for water splitting can include nanofibers of a second semiconductor doped with the nanoparticles of the first semiconductor. The first semiconductor can include a narrow band gap semiconductor, such as ZnS, CdS, CuO, CuS, or In.sub.2O.sub.3. The second semiconductor can include a wide band gap semiconductor, such as TiO.sub.2, ZnO or SnO.sub.2. The polymer solution can include a polymer having a low thermogravimetric analysis (TGA) profile, such as poly(-caprolactone) and an organic solvent.

(8) In an exemplary embodiment, the method of fabricating a photocatalyst for water splitting provided herein includes producing cadmium sulfide (CdS) nanoparticles (NPs), mixing a polymer solution with a solution including a zinc salt to form an electrospinning sol-gel, adding the CdS NPs to the electrospinning sol-gel to provide a colloidal solution; stirring the colloidal solution for a first period of time; electrospinning the colloidal solution after the first period of time to provide electrospun nanofiber (NF) mats; drying the NF mats under vacuum for a second period of time; and calcinating the NF mats to provide the photocatalyst for water splitting. The photocatalyst for water splitting comprises nanofibers of ZnO doped with the nanoparticles of CdS. In an embodiment, the photocatalyst comprises only zinc, cadmium, oxygen, and sulphur.

(9) The polymer solution can include a polymer having a low thermogravimetric analysis (TGA) profile, such as poly(-caprolactone) and an organic solvent, e.g., dimethylformamide (DMF). The solution including a zinc salt can include zinc acetate (ZnAc) and an organic solvent, e.g., dimethylformamide (DMF) (e.g., a solution prepared by adding 1 g of ZnAc to 3 mL of DMF). For example, about 15 mL of poly(-caprolactone) solution can be added to the ZnAc solution and stirred for about three hours at 50 C. to form the clear sol-gel. Once the CdS NPs are added to the sol-gel, the resulting colloidal solution can be stirred continuously for about 5 hours prior to electrospinning. The NF mats formed after electrospinning can be dried under vacuum at about 50 C. for about 24 hours. After drying, the nanofiber mats can be calcined in Ar atmosphere at about 200 C. for about 30 minutes. The poly(-caprolactone) is removed after heating to 200 C. The resulting CdS/ZnO nanofibers can be hexagonal and crystalline in nature.

(10) The composite NFs demonstrated good photocatalytic performance in hydrogen production relative to native ZnO NFs and CdS NPs prepared independently under similar conditions (see the examples in the following detailed description). Hydrogen evolution was approximately 820 molh-1 g-1, 115 molh-1 g-1 and 180 molh-1 g-1 for the composite NFs, native ZnO NFs and CdS NPs, respectively. In addition, the composite NFs exhibited good photostability, possibly due to the nanofibrous morphology facilitating photocarrier transport and increasing active sites on the surface of the photocatalytic materials. The method may be adapted to synthesize other composite nanofibers using the electrospinning technique.

(11) A method for hydrogen production using water splitting can include adding the photocatalyst to an aqueous solution; and irradiating the aqueous solution including the photocatalyst to produce hydrogen. The aqueous solution can include Na.sub.2SO.sub.3 and Na.sub.2S ions. The Na.sub.2SO.sub.3 and Na.sub.2S ions can behave as a hole scavenger for the photocatalyst and/or avoid photo-corrosion. The production of hydrogen can be measured using gas chromatography. The aqueous solution can be irradiated at room temperature. In an embodiment, about 50 mg of the photocatalyst is added to about 50 mL of the aqueous solution. In an embodiment, the photocatalyst is sonicated, e.g., for 30 minutes. In an embodiment, about 820 molh.sup.1g.sup.1 of hydrogen is produced. In an embodiment, the photocatalyst is reusable. For example, the photocatalyst can be used for five consecutive runs, while maintaining excellent stability.

(12) Specific embodiments of the present method of fabricating a photocatalyst for water splitting are illustrated in the following examples. The structure, synthesis and function of an exemplary photocatalyst are also provided in the following examples.

(13) The present teachings are illustrated by the following examples.

Example 1

Preparation of Exemplary CdS/ZnO Nanofibers

(14) CdS NP-doped ZnO NFs were prepared as follows. Dispersed cadmium sulfide (CdS) NPs were prepared by adding an ammonium sulfide ((NH.sub.4).sub.2S) solution (typically 40-48 wt. % in water) to a cadmium acetate (CdAc) solution (e.g., a solution including 1 g of CdAc in 3 mL dimethylformamide (DMF)) under vigorous stirring. An electrospinning solution was prepared by adding 15 mL of poly(-caprolactone) solution (e.g., 7.5 wt. % poly(-caprolactone) in an organic solvent, e.g., DMF) to a zinc acetate (ZnAc) solution (e.g., 1 g of ZnAc in 3 mL DMF). The obtained electrospinning solution was kept under stirring for 3 h at 50 C. to ensure proper mixing and formation of a clear sol-gel. CdS NPs were added to the clear sol-gel to form a colloidal solution. The colloidal solution was kept under continuous stirring for 5 h prior to electrospinning. Electrospinning of the solution provided electrospun NF mats. The electrospun NF mats were dried under vacuum at 50 C. for 24 h and then calcined in Ar atmosphere at 200 C. for 30 min, resulting in the CdS NPs-doped ZnO NFs, which took the form of a powder. For comparison, CdS NPs free of ZnO NFs and ZnO NFs free of CdS NPs were prepared as above and used separately.

Example 2

Photocatalytic Activity Measured

(15) The rate of H.sub.2 production from water splitting catalyzed by the composite NFs, the CdS NPs alone, and the ZnO NFs alone, under visible light was measured in a typical water-filled gas burette system. A 2000 W mercury lamp, fixed at a distance of 10 cm from the burette system, was used as a light source. In each experiment, 50 mg of the catalyst was transferred into a reaction flask having 50 mL of deionized water containing Na.sub.2SO.sub.3 and Na.sub.2S as a sacrificial reagent. The reactor was sealed tightly and sonicated to disperse the photocatalyst completely in the water with sacrificial reagents. To avoid CdS photocorrosion, the gas-burette system was perfused with N.sub.2 gas before starting the reaction in the presence of the sacrificial electron donor to remove any dissolved oxygen. The reaction was conducted under stirring at a rate of 600 rpm and 25 C. The volume of the gas evolved was measured by recording the displacement of water level every minute; the gas passed through the graduated cylinder filled with water containing KOH to estimate the obtained gas and to remove any released SO.sub.2 gas, oxygen and moisture before analysis. The H.sub.2 gas produced was analyzed by a gas chromatograph (GC-2010 Plus, Shimadzu, Ar gas (99%) was used as a carrier gas with flow rate of 20 mLmin.sup.1). The reaction was ceased when no gas was generated. It was observed that no H.sub.2 gas was produced in the absence of either light irradiation or photocatalyst.

(16) FE-SEM images of the electrospun NFs after vacuum drying show that the samples are composed of randomly distributed, smooth surfaced and beads-free NFs with good morphology (FIGS. 1(A) and 1(B)). The calcination of the as-prepared NFs did not affect the nanofibrous morphology (FIGS. 1(C) and 1(D)). Entanglement in the network structure of the NFs without any specific direction was observed. The network structure was highly interconnected with multilayered NFs. The energy dispersive X-ray (EDX) spectroscopic analysis (FIG. 2) of NFs indicates the presence of zinc (Zn), cadmium (Cd), oxygen (O), and Sulphur (S) elements in the spectrum, only. No other elements were detected. The inset to FIG. 2 summarizes the atomic and weight percent of the detected elements.

(17) FIG. 3 shows the XRD patterns of the as-prepared catalysts (NF powder). From the patterns, the standard ZnO diffraction peaks indicate formation of a hexagonal wurtzite structure of ZnO (Sp.Gr P63mc(186), JCPDS 36-1451). In addition, the CdS diffraction peaks indicate the formation of a hexagonal wurtzite structure CdS (Sp.Gr Fm43m(216), JCPDS 10-454). The CdS NP-doped ZnO NFs exhibit a mixture of crystalline phases from the CdS and ZnO.

(18) FIGS. 4A-4D) show TEM, HR-TEM, TEM-EDX and TEM-EDX line-scan images, respectively, for the synthesized NFs. As shown in FIG. 4A, the TEM image indicates that the surface of the composite NF is very rough, which may be due to crystallization of CdS and ZnO. Further, the CdS NPs are completely enveloped into the ZnO NFs. The HR-TEM image of FIG. 4B indicates the presence of parallel atomic planes. Lattice fringes are visible, which are consistent with the lattice spacing planes of hexagonal wurtzite ZnO (JCPDS 36-1451) and hexagonal CdS (JCPDS 10-454), indexed and labeled in FIG. 4B. This finding reveals substantial crystallinity of the composite NFs. This is confirmed by the TEM-EDX line-scan analysis of the line indicated in FIG. 4A, the results of which are shown in FIG. 4D. The TEM-EDX line-scan and spectrum (FIG. 4E) confirms the presence of Zn, Cd, O, and S. The Cd and S appear with a similar distribution, which confirms the formation of CdS, rather than CdSO.sub.4. In addition, Zn and O are the most surface elements in the line-EDX, consistent with the full envelopment of CdS NPs with the ZnO NFs. In other words, CdS NPs are completely covered by ZnO NFs, and are thereby protected from photocorrosion during photocatalytic reaction.

Example 3

Photo-Splitting Assay

(19) The photocatalytic activity of the composite NFs were tested by evaluating H.sub.2 production from an aqueous solution including Na.sub.2SO.sub.3/Na.sub.2S. This salt was used as a hole scavenger for the prepared photocatalyst, as well as to avoid photocorrosion of CdS. No hydrogen was evolved in the presence of the light source and absence of a photocatalyst.

(20) The photocatalytic activity of the composite NFs was compared to the native ZnO NFs and CdS NPs prepared under identical experimental conditions (FIG. 5). Under light irradiation, the ZnO NFs and CdS NPs controls produced a lower amount of H.sub.2 compared to the composite NFs. The composite NFs, ZnO NFs, and CdS NPs produced up to 820 molh.sup.1g.sup.1, 115 molh.sup.1g.sup.1, and 180 molh.sup.1g.sup.1, respectively.

(21) These differences in photocatalytic activity could be due to: the nanofibrous morphology facilitating transport of photocarriers and increasing the surface active sites; high efficiency of visible light absorption; and low recombination rate of photogenerated electron-hole pairs.

(22) The composite NFs exhibited more than twice the photocatalytic activity reported for prior composite core/shell ZnO NFs, which produce only 354 molh.sup.1g.sup.1. This may be due to the formation of pure CdS by the present method rather than Cd.sub.3SO.sub.4 by prior methods.

(23) To evaluate the photo-stability of the prepared composite NFs for practical applications, seven consecutive tests were run under similar conditions, the results of which are shown in FIG. 6. The efficiency of hydrogen evolution decreased modestly with successive cycles. This decrease could be due to consumption of sacrificial electron donating solution. After five consecutive runs, the sacrificial solution was added to make a refresh. Accordingly, the photocatalytic performance reached the original level. These results show excellent stability of the composite NFs as a photocatalyst for hydrogen production.

(24) It is to be understood that the method of fabricating a photocatalyst for water splitting is not limited to the embodiments described above, but encompasses any and all embodiments within the scope of the following claims.