Zun-biao Zhang, Jie Xu, Jing Kang, Yan-xia Chen. Role of Bridge-bonded Formate in Formic Acid Dehydration to CO at Pt Electrode: Electrochemial in-situ Infrared Spectroscopic Study[J]. Chinese Journal of Chemical Physics , 2013, 26(4): 471-476. doi: 10.1063/1674-0068/26/04/471-476
Citation: Zun-biao Zhang, Jie Xu, Jing Kang, Yan-xia Chen. Role of Bridge-bonded Formate in Formic Acid Dehydration to CO at Pt Electrode: Electrochemial in-situ Infrared Spectroscopic Study[J]. Chinese Journal of Chemical Physics , 2013, 26(4): 471-476. doi: 10.1063/1674-0068/26/04/471-476

Role of Bridge-bonded Formate in Formic Acid Dehydration to CO at Pt Electrode: Electrochemial in-situ Infrared Spectroscopic Study

doi: 10.1063/1674-0068/26/04/471-476
Funds:  This work was supported by the National Nat-ural Science Foundation of China (No.21273215) and the National Key Basic Program of China (No.2010CB923302).
  • Received Date: 2013-04-11
  • Formic acid (HCOOH) decomposition at Pt film electrode has been studied by electrochem- ical in situ FTIR spectroscopy under attenuated-total-reflection configuration, in order to clarify whether bridge-bonded formate (HCOOb) is the reactive intermediate for COad for-mation from HCOOH molecules. When switching from HCOOH-free solution to HCOOH-containing solution at constant potential (E=0.4 V vs. RHE), we found that immediately upon solution switch COad formation rate is the highest, while surface coverage of formate is zero, then after COad formation rate decreases, while formate coverage reaches a steady state coverage quickly within ca. 1 s. Potential step experiment from E=0.75 V to 0.35 V, reveals that formate band intensity drops immediately right after the potential step, while the COad signal develops slowly with time. Both facts indicate that formate is not the reactive intermediate for formic acid dehydration to CO.
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Role of Bridge-bonded Formate in Formic Acid Dehydration to CO at Pt Electrode: Electrochemial in-situ Infrared Spectroscopic Study

doi: 10.1063/1674-0068/26/04/471-476
Funds:  This work was supported by the National Nat-ural Science Foundation of China (No.21273215) and the National Key Basic Program of China (No.2010CB923302).

Abstract: Formic acid (HCOOH) decomposition at Pt film electrode has been studied by electrochem- ical in situ FTIR spectroscopy under attenuated-total-reflection configuration, in order to clarify whether bridge-bonded formate (HCOOb) is the reactive intermediate for COad for-mation from HCOOH molecules. When switching from HCOOH-free solution to HCOOH-containing solution at constant potential (E=0.4 V vs. RHE), we found that immediately upon solution switch COad formation rate is the highest, while surface coverage of formate is zero, then after COad formation rate decreases, while formate coverage reaches a steady state coverage quickly within ca. 1 s. Potential step experiment from E=0.75 V to 0.35 V, reveals that formate band intensity drops immediately right after the potential step, while the COad signal develops slowly with time. Both facts indicate that formate is not the reactive intermediate for formic acid dehydration to CO.

Zun-biao Zhang, Jie Xu, Jing Kang, Yan-xia Chen. Role of Bridge-bonded Formate in Formic Acid Dehydration to CO at Pt Electrode: Electrochemial in-situ Infrared Spectroscopic Study[J]. Chinese Journal of Chemical Physics , 2013, 26(4): 471-476. doi: 10.1063/1674-0068/26/04/471-476
Citation: Zun-biao Zhang, Jie Xu, Jing Kang, Yan-xia Chen. Role of Bridge-bonded Formate in Formic Acid Dehydration to CO at Pt Electrode: Electrochemial in-situ Infrared Spectroscopic Study[J]. Chinese Journal of Chemical Physics , 2013, 26(4): 471-476. doi: 10.1063/1674-0068/26/04/471-476

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