Abstract:
A titanium dioxide coating method is disclosed. An electrolyte containing Ti 3+ , an oxidant, and at least one of NO 3   −  and NO 2   −  is provided for an electrodeposition device, wherein the oxidant is configured for essentially oxidizing Ti 3+  into Ti 4+ . A substrate is immersed into the electrolyte and electrically connected to the electrodeposition device. A cathodic current is applied to the substrate via the electrodeposition device for reduction of NO 2   −  or NO 3   − . A titanium dioxide film is thus formed on the surface of the substrate. The thickness, porosity, and morphology of the titanium dioxide film can be controlled by varying the electroplating parameters, and relatively uniform deposits on various substrates of complex shapes can be obtained by use of low cost instruments. The resultant structure of Ti 4+  species oxidized from Ti 3+  by the oxidant can be used to control the deposition rate of TiO 2 .

Description:
RELATED APPLICATIONS 
       [0001]    This application is a Continuation-in-part of co-pending application Ser. No. 12/505,936 filed on Jul. 20, 2009. 
     
    
     BACKGROUND OF THE INVENTION 
       [0002]    1. Field of the Invention 
         [0003]    The present invention relates to a titanium dioxide coating method and the electrolyte used therein, and more particularly to an electrodeposition method for coating titanium dioxide and the electrolyte used therein. 
         [0004]    2. Description of the Prior Art 
         [0005]    Titanium dioxide, also known as titania, is widely recognized as an important electrode material in semiconductor photo-electrochemistry. Among the three main crystalline phases: anatase, rutile, and brookite TiO 2 , the anatase form (A-TiO 2 ) is the most popular photo-electrode because the lowest unoccupied molecular orbital of dyes, such as N719, is very close to the conduction band of A-TiO 2 . 
         [0006]    In addition, A-TiO 2  generally shows relatively high reactivity and chemical stability under ultraviolet light excitation for water and air purifications, photocatalysts, gas sensors, electrochromic devices, and so on, further emphasizing its practical importance. 
         [0007]    Several techniques were proposed for fabricating TiO 2 , such as sol-gel, chemical vapor deposition, hydrothermal, electrospinning, anodizing, and electrodeposition. 
         [0008]    Among these methods, cathodic deposition of TiO 2  becomes attractive because electrochemical deposition provides the advantages of controlling the thickness and morphology by varying the electroplating parameters, relatively uniform deposits on complex shapes, and use of low cost instrumentation. 
         [0009]    Sotiropoulos et al. (Electrochimica Acta 51 (2006) 2076-2087) prepared TiO2 films from acidic aqueous solutions of TiOSO 4  and H 2 O 2  by room temperature potentiostatic cathodic electrosynthesis. However, Sotiropoulos taught that TiOSO 4  was oxidized to Ti 6+  by using a strong oxidant H 2 O 2 , which needs to be reduced to prepare the TiO 2  film. 
         [0010]    Kim et al. (Electrochimica Acta 50 (2005) 2713-2718) taught a novel approach using TiCl 3  or TiCl 4  as the precursors for the electrodeposition of TiO 2  films. Kim mainly focused on the advantage in using CTAB and the pH value of the solution is roughly 3 in all the cases (Kim, p. 2714 Experimental section 2, paragraph 2). 
         [0011]    Both of Sotiropoulos and Kim did not achieve high yield of titanium dioxide and it is now a current goal to develop a cathodic deposition method for coating titanium dioxide with higher yield in comparison with the prior arts. 
       SUMMARY OF THE INVENTION 
       [0012]    The present invention is directed to provide an electrolytic method for coating titanium dioxide to gain the advantages of controlling the thickness, porosity, and morphology by varying the electroplating parameters, relatively uniform deposits on various substrates of complex shapes, and use of low cost instrumentations. 
         [0013]    The present invention is directed to a cathodic deposition method for coating a titanium dioxide film with higher yield in comparison with the prior arts. 
         [0014]    According to one embodiment, the present invention provides a titanium dioxide coating method, which includes following steps. An electrolyte containing Ti 3+ , an oxidant and at least one of NO 3   −  and NO2 −  is provided for an electrodeposition device, wherein the oxidant is configured for essentially oxidizing Ti 3+  into Ti 4+ . A substrate is immersed into the electrolyte and electrically connected to the electrodeposition device. A cathodic current from the electrodeposition device is applied to the substrate for reducing NO 2   −  or NO 3   −  to generate extensive OH −  and to form titanium dioxide film on the surface of the substrate. 
         [0015]    Other advantages of the present invention will become apparent from the following descriptions taken in conjunction with the accompanying drawings wherein are set forth, by way of illustration and example, certain embodiments of the present invention. 
     
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         [0016]    The foregoing aspects and many of the accompanying advantages of this invention will become more readily appreciated as the same becomes better understood by reference to the following detailed description, when taken in conjunction with the accompanying drawings, wherein: 
           [0017]      FIG. 1  illustrates a flowchart of a titanium dioxide coating method according to one embodiment of the present invention; 
           [0018]      FIG. 2  illustrates LSV (linear sweep voltammetry) curves according to one embodiment of the present invention; 
           [0019]      FIG. 3A  illustrates first and second scans of LSV curves according to one embodiment of the present invention; 
           [0020]      FIG. 3B  illustrates the corresponding EQCM (electrochemical quartz crystal microbalance) responses of the first and second scans of LSV in  FIG. 3A  according to one embodiment of the present invention; 
           [0021]      FIG. 3C  illustrates an enlarged view of curve  1  in  FIG. 3B ; 
           [0022]      FIG. 3D  illustrates a SEM image of titanium dioxide depth for 3 cycles according to one embodiment of the present invention. 
           [0023]      FIGS. 4A and 4B  illustrate SEM (Scanning Electron Microscope) images according to one embodiment of the present invention; 
           [0024]      FIGS. 4C and 4D  illustrate TEM (Transmission Electron Microscope) images according to one embodiment of the present invention; 
           [0025]      FIGS. 4E and 4F  illustrate depth profiles of XPS (X-ray photoelectron spectra) according to one embodiment of the present invention; 
           [0026]      FIG. 5A  illustrates the LSV curves according to one embodiment of the present invention; 
           [0027]      FIG. 5B  illustrates the corresponding EQCM (electrochemical quartz crystal microbalance) responses of the LSV curves in  FIG. 5A  according to one embodiment of the present invention; and 
           [0028]      FIG. 5C  illustrates the dependence of TiO 2  mass on the cycle number of CV according to one embodiment of the present invention. 
       
    
    
     DESCRIPTION OF THE PREFERRED EMBODIMENT 
       [0029]      FIG. 1  illustrates a flowchart of a titanium dioxide coating method including following steps. Beginning at step S 1 , an electrolyte with pH values ≦2 and containing Ti 3+ , an oxidant and at least one of NO 3   −  and NO 2   − . The Ti 3+  is essentially oxidized into Ti 4+  by the oxidant and NO 3   − /NO 2   −  is the OH −  provider. This electrolyte is provided for an electrodeposition device. Next, at step S 2 , a substrate is then immersed into the electrolyte and at step S 3 , the substrate is electrically connected to the electrodeposition device. At step S 4 , a cathodic current is applied on the substrate via the electrodeposition device for reducing NO 2   −  or NO 3   −  to generate extensive OH −  for depositing TiO 2  films on the surface of substrates. The cathodic current can be applied by galvanostatic (constant dc current), potentiostatic (constant voltage), potentiodynamic, or galvanodynamic methods, or in the pulse voltage or pulse current modes. 
         [0030]    In one preferred embodiment, an electrolyte with pH values &lt;1 is provided for titanium dioxide deposition. Ti 3+  may be obtained from dissolution of titanium, for example by dissolving with H 2 O 2  and ammonia. 
         [0031]    The oxidants can be divided into two groups, strong and weak oxidants. When the weak oxidants are employed, Ti 3+  can only be oxidized to Ti 4+ , even excess oxidants are added. When the strong oxidants are employed, a stoichiometric ratio between Ti 3+  and oxidants is required to oxidize Ti 3+  to Ti 4+  which cannot be further oxidized to Ti 6+ . Referring to Table 1, weak oxidants that essentially oxidize Ti 3+  into Ti 4+  are provided and include without limitations to NO 3   − , NO 2   − , S 2 O 8   2− , ClO 4   − , ClO − , BrO 4   − , BrO − , IO 4   −  or IO − . The strong stoichiometric oxidants include without limitations to H 2 O 2  or O 3 . 
         [0000]    
       
         
               
             
               
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Oxidants that essentially oxidize Ti 3+  into Ti 4+   
               
             
          
           
               
                   
                 Oxidant 
                 Ti 3+ →Ti 4+   
                   @ Ti 4+ →Ti 6+   
                 Color 
               
               
                   
                   
               
               
                   
                 NO 3   −   
                 Yes 
                 No 
                 transparent 
               
               
                   
                 NO 2   −   
                 Yes 
                 No 
                 transparent 
               
               
                   
                 *XO 4   −   
                 Yes 
                 No 
                 transparent to 
               
               
                   
                   
                   
                   
                 pale yellow %   
               
               
                   
                 *XO −   
                 Yes 
                 No 
                 transparent to 
               
               
                   
                   
                   
                   
                 pale yellow %   
               
               
                   
                 S 2 O 8   −   
                 Yes 
                 No 
                 transparent to 
               
               
                   
                   
                   
                   
                 pale yellow %   
               
               
                   
                 H 2 O 2   
                 Yes #   
                 Yes 
                 Tangerine 
               
               
                   
                 O 3   
                 Yes #   
                 Yes 
                 Tangerine 
               
               
                   
                   
               
               
                   
                 *X represents Cl, Br, I 
               
               
                   
                   # Stoichiometric ratio 
               
               
                   
                   @ excess oxidant 
               
               
                   
                   % turning pale yellow when excess oxidant is present 
               
             
          
         
       
     
         [0032]    The continuous reduction of NO 2   −  or NO 3   −  to N 2  and NH 3  generates extensive OH − , and effectively enhances the deposition of TiO 2  films on the surface of substrates. 
         [0033]    In one embodiment, a post annealing step is further performed after forming the titanium dioxide film on the surface of the substrate, wherein the post annealing step is carried out at about 100-800° C. 
         [0034]    The following descriptions of specific embodiments of the present invention have been presented for purposes of illustrations and description, and they are not intended to be exclusive or to limit the present invention to the precise forms disclosed, and obviously many modifications and variations are possible in light of the above teaching. It is intended that the scope of the invention can be defined by the Claims appended hereto and their equivalents. 
         [0035]    TiO 2  particulates are cathodically deposited onto graphite substrates from an electrolyte bath containing 0.47 M HCl, 25 mM TiCl 3  and 75 mM NaNO 3  in an electrodeposition device according to an embodiment of the present invention. A pretreatment procedure of graphite substrates may be performed and the detailed description thereof is herein omitted. 
         [0036]    According to one embodiment of the present invention, the redox reaction between Ti 3+  and NO 3   −  during preparation of the deposition solution is herein disclosed. Nitrates, acting as the oxidizers, were reduced to NO 2  (reddish-brown bubbles) when the transparent NaNO 3  solution was added into the purple TiCl 3  solution. Since NO 2  molecules are soluble in acidic aqueous media, they will automatically convert into NO 3   −  and NO. This statement is supported by the observation that reddish-brown bubbles gradually disappear within 30-40 seconds and the purple TiCl 3  solution in presence of Ti 3+  is a colorless transparent solution indicating the formation of TiO 2+  (see equations 1 and 2) 
         [0000]      Ti 3+ +NO 3− →TiO 2+ +NO 2   (1)
 
         [0000]      3NO 2 +H 2 O→2HNO 3 +NO  (2)
 
         [0037]    Curves  1 - 5  in  FIG. 2  correspond to the i-E responses measured from various electrolytes. As can be seen from curves  1  and  2 , reduction commences at potentials negative to −0.6 V and no gas evolution is found at potentials positive to −0.6 V. However, a rapid generation of many bubbles is clearly observed when potentials are negative to −0.6 V, indicating H 2  evolution. On curves  3  and  4 , reduction starts in the more positive potential region, revealing the facile reduction of NaNO 2 . In addition, minor gas evolution commences from 0.4 V to −0.4 V with a low current density, while gas evolution ceases in the potential range from −0.4 V to −1.2 V and occurs dramatically again at potentials behind −1.2 V. The above results indicate that NO 2   −  is responsible for the reduction in the more positive potential region with minor gas evolution, presumably due to the reduction of NO 2   −  into N 2  molecules. Since gas evolution temporarily disappears in the potential range from −0.4 V to −1.2 V. This result suggests a further reduction of N 2  to NH 4   +  in such a negative potential range (see equations 3 and 4). 
         [0000]      2NO 2   − +4H 2 O+6e→N 2 +8OH −   (3)
 
         [0000]      N 2 +8H 2 O+6e→2NH 4   + +8OH −   (4)
 
         [0038]    On curve  5 , gas evolves gently at about −0.1 V, disappears at ca. −0.4 V and, dramatically evolves again at potentials negative to −1.2 V, which completely follows the gas evolution-disappearance phenomena measured from the solution containing NO 2   − . Based on equations 1 and 2, reduction of NO 3   −  in the designed deposition bath for generating concentrated OH −  at the vicinity of electrode surface is very similar to the reduction of NO 2   −  (see equation 5). Accordingly, reduction of NO 2   −  or NO 3   −  is concluded to be an effective step in promoting the deposition of TiO(OH) 2  (see equation 6). The TiO(OH) 2  is then dehyrated to form TiO 2  (see equation 7). 
         [0000]      2NO 3   − +6H 2 O+10e→N 2 +12OH −   (5)
 
         [0000]      TiO 2+ +2OH − +xH 2 O→TiO(OH) 2 .xH 2 O  (6)
 
         [0000]      TiO(OH) 2 .xH 2 O→TiO 2 +(x+1)H 2 O  (7)
 
         [0039]    The mechanism proposed in this invention not only reasonably interprets the gas evolution/disappearance phenomena but also explains the slight increase in bath pH after the deposition, which is different from the slight decrease in pH found in previous case of NO 3   −  reduction. Based on equations 3, 4, and 6, OH −  is mainly provided by the NO 2   −  or NO 3   −  reduction and the consequent N 2  reduction, resulting in the generation of NH 4   + . As a result, a slight increase in pH found in this formulated solution after TiO 2  deposition is reasonable because the OH − / electron ratios for the reduction of NO 2   − , NO 3   − , and N 2  are equal to 4/3, 6/5, and 4/3, respectively, which are larger than the proton/electron ratio (equal to 1) for oxygen evolution at the anode. Moreover, the deposition rate in this formulated solution is very fast, attributable to the massive generation of OH − , the catalytic reduction of NO 2   −  and NO 3   −  by TiO(OH) 2  and TiO 2 , and the guarantee of TiO 2+  formation via the redox reaction between Ti 3+  and oxidants such as NO 3   − /NO 2   − . 
         [0040]      FIG. 3A  illustrates the first and second scans of LSV (linear sweep voltammetry) curves and  FIG. 3B  illustrates the corresponding EQCM (electrochemical quartz crystal microbalance) responses of the first and second scans of LSV measured from the designed solution in order to precisely obtain the onset potential of deposition. A comparison of the i-E and mass-E responses indicates that there is always an incubation period for N 2  evolution in the positive potential range, e.g., from 0.2 to −0.7 V and from 0.1 to −0.65 V for the first and second sweeps, respectively. Although in the incubation range, NO 2   −  and NO 3   −  start to be reduced to N 2 , no significant increase in mass is observed. The slight weight gain in this potential region is probably due to the NO 2   − /NO 3   −  adsorption at the cathode. Based on the EQCM result, once the potential is negative enough to generate/accumulate concentrated OH − , TiO 2+  will combine with OH −  to form TiO 2  and an obvious weight gain is visible behind this onset potential of deposition (−0.85 and −0.65 V for the first and second scans, respectively). Also note the positive shift in the onset potential of deposition during the second scan. This phenomenon is probably due to the electrocatalytic property of TiO(OH) 2  and TiO 2  already deposited onto the graphite surface during the first scan for NO 3   − /NO 2   − /N 2  reduction. 
         [0041]    Referring to  FIG. 3D , the present invention achieve ca. 20 μm (5.4, 7.4 and 7.6 μm for 3 cycles). The dashed lines in  FIG. 3D  indicate the boundary between deposit and substrate as well as the boundaries of TiO 2  deposits between each CV cycle, respectively. The catalytic effect of TiO(OH) 2  and TiO 2  for the NO 3   − , NO 2   − , and N 2  reduction is also one of the main reasons why the present invention achieved a much higher yield of titanium dioxide (in comparison to 4 μm for 20 cycles for Kim et al.). In addition, the usage of weak oxidants, such as NO 3   −  and NO 2   −  even in excess, guarantees the formation of TiO 2+ , which is also one of the main reasons why the present invention achieved a much higher yield of titanium dioxide. 
         [0042]    The electrodes were cleaned in an ultrasonic DI water bath and dried under a cool air flow after cathodic deposition. After cleaning and drying, some electrodes were annealed at 400° C. in air for 1 hr. The morphologies were examined by a FE-SEM (Field-Emission Scanning Electron Microscope, FE-SEM). The EQCM study was performed by an electrochemical analyzer, CHI 4051A in a one-compartment cell. The microstructure and SAED (selected area electron diffraction, SAED) patterns of as-deposited and annealed TiO 2  deposits were observed through a TEM (FEI E.O Tecnai F20 G2). The depth profiles of Ti and O were measured by an X-ray photoelectron spectrometer (XPS, ULVAC-PHI Quantera SXM), employed Al monochromator (hv=1486.69 eV) irradiation as the photosource. 
         [0043]    It is favorable to prepare porous A-TiO 2  films by combining cathodic deposition from this designed solution with lower pH value and post-deposition annealing. As illustrated in  FIGS. 4A and 4B , TiO 2  films before and after annealing are porous and the particle size is roughly estimated to be 60-100 nm. The porous nature of TiO 2  films prepared in this invention is probably due to the extensive tiny bubble evolution during the deposition. The particulates are considered as aggregates of TiO 2  primary particles. 
         [0044]    The average size for as-deposited TiO 2  primary particles is about 6 nm, which is enlarged by post-deposition annealing (ca. 10 nm for TiO 2  annealed at 400° C.) from  FIGS. 4C and 4D . The lattice clearly visible in  FIG. 4D  and the diffraction rings in its inset indicate the anatase structure which is transformed from the amorphous, as-deposited TiO 2  by post-deposition annealing.  FIGS. 4E and 4F  illustrate the depth profiles of Ti, O, and C for as-deposited and annealed samples. Clearly, the atomic ratio of Ti/O is approximately constant (ca. 1/2) within the whole oxide matrix. 
         [0045]    These results confirm the formation of TiO 2  in the as-prepared and annealed films. Accordingly, combining cathodic deposition from this designed solution and post-deposition annealing is favorable for preparation of porous A-TiO 2  films. 
         [0046]    The aforementioned embodiment exemplified the reaction from the electrolyte solution containing Ti 3++  NO 3   − ; however, the redox reaction between Ti 3+  and NO 2   −  in an electrolyte solution can be used for depositing titanium dioxide films, too (See Equations 3, 4, 6, and 8). 
         [0000]      6Ti 3+ +2NO 231  +2H 2 O→6TiO 2+ +N 2 +4H +   (8)
 
         [0047]      FIGS. 5A and 5B  show the typical LSV and Δm-E curves measured at 25 mV s −1  from 0 to −1.6 V (vs. Ag/AgCl) in diluted baths A and B, respectively. Bath A is defined as a deposition solution containing 30 mM H 2 O 2 , 60 mM TiCl 3 , and 75 mM NaNO 3 . Bath B is defined as a deposition solution containing 60 mM TiCl 3  and 135 mM NaNO 3 . In  FIG. 5A , the onset potential of reduction on both i-E curves is the same, −0.47 V, which is reasonably due to the same reaction, NO 3   −  reduction on the EQCM electrode. The reduction currents on curve  1  are always higher than that on curve  2  at any specified potentials negative to −0.47 V although the concentration of NO 3  in both baths should be the same under the assumption that most NO 2  gases generated in bath B are not dissolved in the deposition bath. Accordingly, the formation of certain Ti 4′  hydroxyl species (e.g., 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    in bath A is favorable for the NO 3   −  reduction. 
         [0048]    Referring to  FIG. 5B , the mass of TiO 2  increases sharply from 0 to 70 ng in the potential region between −0.71 and −0.8 V and then, a gradual increase to 145 ng at potentials negative to −0.8 V on curve  1 . On curve  2 , significant increase in mass commences at ca. −0.68 V and then, a shoulder is found between −0.68 and −0.9 V. After that, a sharp increase in mass occurs from −0.9 to −1.0 V and a gradual increase from 70 to 130 ng at potentials negative to −1.0 V. Clearly, the TiO 2  deposition rate in bath A is obviously higher than that in bath B, attributable to the formation of Ti 4+  hydroxyl species containing bridged OH groups in the solution. Such Ti 4+  hydroxyl species (with olation) need fewer OH −  to form the polymeric oxy-hydroxyl Ti precipitates which will be converted to TiO 2  through dehydration. Accordingly, the formation of Ti 4+  hydroxyl dimmers containing bridged OH groups favors the cathodic deposition of TiO 2 . 
         [0049]    Referring to  FIG. 5C , Lines 1 and 2 show the dependence of TiO 2  mass on the cycle number of CV between 0 and −1.6 V from baths A and B, respectively. Clearly, the dependence of TiO 2  mass on the cycle number of CV from both deposition baths is linear. However, the slope of curve  1  is obviously higher than that of curve  2 , revealing that the deposition solution containing H 2 O 2  is more favorable for the cathodic deposition of TiO 2  in comparison with that containing NO 3   −  only. Hence, the resultant structure of Ti 4+  species oxidized from Ti 3+  by the oxidant determines the deposition rate of TiO 2 . 
         [0050]    To sum up, a titanium dioxide coating method according to the present invention includes a cathodic deposition using an electrolytic solution containing Ti 3+ , an oxidant, and at least one of NO 3   −  and NO 2   − , and a post-deposition annealing process, which is favorable for preparing porous A-TiO 2  films. The redox reaction between Ti 3+  and oxidant to form Ti 4+  prior to cathodic deposition effectively promotes the TiO 2  deposition. The resultant structure of Ti 4+  species oxidized from Ti 3+  by the oxidant determines the deposition rate of TiO 2 . The continuous reduction of NO 2   −  or NO 3   −  to N 2  and NH 3  generates extensive OH −  and effectively enhances the deposition of TiO 2  for forming a TiO 2  film at the substrate surface. 
         [0051]    The porous, anatase structure of annealed TiO 2 , examined by FE-SEM, TEM, and SAED analyses is expected to be good for the dye-sensitized solar cell (DSSC) application. In addition, A-TiO 2  may be applicable for water and air purifications, photocatalysts, gas sensors, electrochromic devices, and so on. 
         [0052]    While the invention is susceptible to various modifications and alternative forms, a specific example thereof has been shown in the drawings and is herein described in detail. It should be understood, however, that the invention is not to be limited to the particular form disclosed, but to the contrary, the invention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the appended claims.