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Title: Water–Gas Shift Reaction on K/Cu(111) and Cu/K/TiO 2(110) Surfaces: Alkali Promotion of Water Dissociation and Production of H 2

Abstract

The addition of potassium atoms to Cu(111) and Cu/TiO 2(110) surfaces substantially enhances the rate for water dissociation and the production of hydrogen through the water–gas shift reaction (WGS, CO + H 2O → H 2 + CO 2). In the range of temperatures investigated, 550–625 K, Cu/K/TiO 2(110) exhibits a WGS activity substantially higher than those of K/Cu(111), Cu(111), and Cu/ZnO(0001̅) systems used to model an industrial Cu/ZnO catalyst. The apparent activation energy for the WGS drops from 18 Kcal/mol on Cu(111) to 12 Kcal/mol on K/Cu(111) and 6 Kcal/mol on Cu/K/TiO 2(110). The results of density functional calculations show that K adatoms favor the thermochemistry for water dissociation on Cu(111) and Cu/TiO 2(110) with the cleavage of an O–H bond occurring at room temperature. Furthermore, at the Cu/K/TiO 2 interface, there is a synergy, and this system has a unique ability to dissociate the water molecule and catalyze hydrogen production through the WGS process. In conclusion, when optimizing a regular catalyst, it is essential to consider mainly the effects of an alkali promoter on the metal–oxide interface.

Authors:
ORCiD logo [1];  [2];  [3];  [4]; ORCiD logo [5];  [2]; ORCiD logo [5]; ORCiD logo [2]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States); SUNY Stony Brook, Stony Brook, NY (United States)
  2. Univ. de Sevilla, Sevilla (Spain)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States); Univ. Central de Venezuela, Caracas (Venezuela); Zoneca-CENEX, R&D Labs, Monterrey, (Mexico)
  4. SUNY Stony Brook, Stony Brook, NY (United States)
  5. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1572352
Report Number(s):
BNL-212267-2019-JAAM
Journal ID: ISSN 2155-5435
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Name: ACS Catalysis; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY

Citation Formats

Rodriguez, José A., Remesal, Elena R., Ramírez, Pedro J., Orozco, Ivan, Liu, Zongyuan, Graciani, Jesus, Senanayake, Sanjaya D., and Sanz, Javier Fernandez. Water–Gas Shift Reaction on K/Cu(111) and Cu/K/TiO2(110) Surfaces: Alkali Promotion of Water Dissociation and Production of H2. United States: N. p., 2019. Web. doi:10.1021/acscatal.9b03922.
Rodriguez, José A., Remesal, Elena R., Ramírez, Pedro J., Orozco, Ivan, Liu, Zongyuan, Graciani, Jesus, Senanayake, Sanjaya D., & Sanz, Javier Fernandez. Water–Gas Shift Reaction on K/Cu(111) and Cu/K/TiO2(110) Surfaces: Alkali Promotion of Water Dissociation and Production of H2. United States. doi:10.1021/acscatal.9b03922.
Rodriguez, José A., Remesal, Elena R., Ramírez, Pedro J., Orozco, Ivan, Liu, Zongyuan, Graciani, Jesus, Senanayake, Sanjaya D., and Sanz, Javier Fernandez. Thu . "Water–Gas Shift Reaction on K/Cu(111) and Cu/K/TiO2(110) Surfaces: Alkali Promotion of Water Dissociation and Production of H2". United States. doi:10.1021/acscatal.9b03922.
@article{osti_1572352,
title = {Water–Gas Shift Reaction on K/Cu(111) and Cu/K/TiO2(110) Surfaces: Alkali Promotion of Water Dissociation and Production of H2},
author = {Rodriguez, José A. and Remesal, Elena R. and Ramírez, Pedro J. and Orozco, Ivan and Liu, Zongyuan and Graciani, Jesus and Senanayake, Sanjaya D. and Sanz, Javier Fernandez},
abstractNote = {The addition of potassium atoms to Cu(111) and Cu/TiO2(110) surfaces substantially enhances the rate for water dissociation and the production of hydrogen through the water–gas shift reaction (WGS, CO + H2O → H2 + CO2). In the range of temperatures investigated, 550–625 K, Cu/K/TiO2(110) exhibits a WGS activity substantially higher than those of K/Cu(111), Cu(111), and Cu/ZnO(0001̅) systems used to model an industrial Cu/ZnO catalyst. The apparent activation energy for the WGS drops from 18 Kcal/mol on Cu(111) to 12 Kcal/mol on K/Cu(111) and 6 Kcal/mol on Cu/K/TiO2(110). The results of density functional calculations show that K adatoms favor the thermochemistry for water dissociation on Cu(111) and Cu/TiO2(110) with the cleavage of an O–H bond occurring at room temperature. Furthermore, at the Cu/K/TiO2 interface, there is a synergy, and this system has a unique ability to dissociate the water molecule and catalyze hydrogen production through the WGS process. In conclusion, when optimizing a regular catalyst, it is essential to consider mainly the effects of an alkali promoter on the metal–oxide interface.},
doi = {10.1021/acscatal.9b03922},
journal = {ACS Catalysis},
number = ,
volume = ,
place = {United States},
year = {2019},
month = {10}
}

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This content will become publicly available on October 17, 2020
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