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Dispersive XAFS Study on the Laser-Induced Reduction of a Rh$$^{3+}$$ ion complex; Presence of a Rh$$^{+}$$ Intermediate in Direct Photoreduction

Saeki, Morihisa*; Matsumura, Daiju   ; Nakanishi, Ryuzo*; Yomogida, Takumi   ; Tsuji, Takuya  ; Saito, Hiroyuki*; Oba, Hironori* 

The reaction mechanism of the direct photoreduction of a Rh$$^{3+}$$ ion complex to a Rh$$^{0}$$ species induced by pulsed ultraviolet laser irradiation was studied using dispersive X-ray absorption fine structure (DXAFS) spectroscopy. The time-resolved X-ray absorption near edge structure (XANES) showed the absence of isosbestic points and suggested that more than two Rh$$^{n+}$$ species contribute toward the direct photoreduction of Rh$$^{3+}$$. Analysis of the time-resolved XANES data by singular value deposition showed that the direct photoreduction involves three Rh$$^{n+}$$ species. Multivariate curve resolution by alternating least-squares analysis (MCR-ALS) of the time-resolved XANES data gave pure spectra and concentration profiles of the three Rh$$^{n+}$$ species. The Rh$$^{n+}$$ species were assigned to Rh$$^{3+}$$, Rh$$^{+}$$, and Rh$$^{0}$$ species based on the features of the pure XANES spectra. The concentration profiles suggested that the direct photoreduction proceeds in the order of Rh$$^{3+}$$ $$rightarrow$$ Rh$$^{+}$$ $$rightarrow$$ Rh$$^{0}$$. A reaction mechanism, which was proposed involving photoreductions of Rh$$^{3+}$$ and Rh$$^{+}$$, photoinduced autocatalytic reductions of Rh$$^{3+}$$ and Rh$$^{+}$$, and photooxidation of Rh$$^{+}$$, well reproduced the concentration profiles of three Rh$$^{n+}$$ species.

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