Page 6 - Shimadzu Lightway
P. 6

Measuring Photon Count Accurately                                                                                         Applications



            Previously, a chemical actinometer was required to calculate the number of irradiated photons,                            Various applications using the system are described below.
            but there were concerns about variability caused by the chemical actinometer adjustment                                   (Measured by: Associate Professor Yusuke Tamaki of the Department
            process. The Lightway  system uses a power meter to calibrate the number of irradiated                                    of Chemistry, Graduate School of Science and Engineering, Tokyo
                               ™
            photons and make corrections based on spectral shape prior to measuring, which prevents
            variability caused by differences in skill levels.                                                                        Institute of Technology)
                  It also features a stable and long-lasting LED irradiation light source.




            Using an LED irradiation light source means reliable measurements can be obtained                                                         Using a Ru-Re Supramolecular Complex Photocatalyst to Measure
            over long periods.
                                                                                                                                                           Photoreaction Quantum Yield of CO2 Reduction Reaction
            100
                                                                                                                                      ●Measuring Photoreaction Quantum Yield
                 Intensity decreases                                                                                                  A Ru-Re supramolecular complex photocatalyst (Fig. 1) was used to measure the quantum yield of a carbon dioxide reduction
                during measurements.
              Relative Intensity  Recommended  Reliable measurements                                                                  reaction. The sample was irradiated with 17 × 10  einstein·s  of 470 nm light and then the absorption spectrum and number of
                                                                                                                                                                            -9
                                                                                                                                                                                     -1
                                                                                                                                      photons absorbed were measured. Carbon monoxide generated from the reduction reaction was then quanti ed using a gas
                                                                                                                                      chromatograph. The graph in Fig. 2 correlating the quantity of carbon monoxide generated to the number of photons
                   service life
                                                                                                                                      the given experiment.
                        Replacement                                                                                                   absorbed was obtained. Since the reaction quantum yield corresponds to the slope in Fig. 2, a result of 40 % was obtained for
                                                                              LED
                                                                              Xenon lamp                                                                                                           14
               0          1000       2000        3000       4000        5000
                                         Time  (hr.)                                                                                                                                               12
            The  gure above illustrates one example of how light source intensity decreases over time. The red line indicates the intensity of an              n+                                  10     ФCO=40%
            LED irradiation light source, whereas the blue line indicates the intensity of a xenon lamp irradiation light source. It shows that the               / hv                             CO/µmol  8
            LED irradiation light source offers high intensity for a longer time and the intensity decrease is more gradual than for the xenon lamp               λex  = 470 nm  -1                 6
                                                                                                                                                                       -9
            irradiation light source.                                                                                                   CO2         (50 µM)        17×10  einstein・s  CO            4
                                                                                                                                                                                                    2
                                                                                                                                                          in DMF-TEOA (5:1 v/v)                     0
            An optional LED irradiation light source is        The LED irradiation light source can be                                           BIH (0.1 M)                                        0.00  0.25  0.50  0.75  1.00  1.25  1.50  1.75  2.00
                                                                                                                                                                                                                          19
            available.*                                        replaced easily.                                                                                                                       Absorbed Photon Number/10
                                                                                                                                      Fig. 1 Diagram of Ru-Re Supramolecular Complex Photocatalyst Reaction  Fig. 2 Quantity of Carbon Monoxide Generated vs.
                                                                                                                                                                                                       Number of Photons Absorbed
              1.2
                                                               Remove base and LED lamp from main unit.
                       365 nm  405 nm  460 nm   550 nm
               1
                                                                                                                                      ●Measuring Intermediates
                                                                                                                                      An attempt was made to directly observe intermediates during the carbon dioxide photoreduction reaction of a Ru-Re supramolecu-
              0.8
                                                                                                                                      lar complex photocatalyst (Fig. 1). Time-course changes in absorption spectra measured during the photocatalytic reaction are
             a.u.  0.6                                                                                                                shown in Fig. 3. Difference spectra with respect to the absorption spectrum measured at the start of measurement are shown in Fig.
                                                                                                                                      4. The new absorption observed near 550 nm in Fig. 3 and Fig. 4 is due to the absorption spectra of intermediates. A comparison to
              0.4
                                                                                                                                      previously reported data con rmed that the intermediates are one-electron reduced species from a photoelectron-transfer reaction
              0.2                                                                                                                     of the Ru-Re supramolecular complex photocatalyst.
                                                                                                                                                  0.8                                                 0.15
               0
               300    350   400    450    500    550   600
                                                                                                                                                                                                                       Direction of
                                Wavelength (nm)                                                                                                   0.6
                                                                                                                                                                                                       0.1             reaction
            * This product is manufactured by CELL System Co., Ltd. Therefore,
                                                                                                                                                 Absorbance  0.2  Direction of                       △Absorbance  0.05
               it must be purchased as an optional product.                                                                                       0.4
                                                                                                                                                                reaction
                                                                                                                                                                                                        0
                                                                                                                                                   0
                                                                                                                                                                                                      -0.05
                                                                                                                                                   400     500     600     700                         400     500     600     700
                                                                                                                                                          Wavelength / nm                                      Wavelength / nm
                                                                                                                                             Fig. 3 Ru-Re Supramolecular Complex Photocatalyst   Fig. 4 Ru-Re Supramolecular Complex Photocatalyst
                                                               Install new LED lamp with base into the main unit.                                Reaction Spectral Measurement Results             Reaction Difference Spectra Calculation Results

                                                                                                                                                                                                                             Lightway
      6                                                                                                                                                                                                                 PQY-01 Photoreaction Evaluation System  7
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