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Title: Visible and near-infrared photothermal catalyzed hydrogenation of gaseous CO 2 over nanostructured Pd@Nb 2O 5

Abstract

The reverse water gas shift (RWGS) reaction driven by Nb 2O 5 nanorod-supported Pd nanocrystals without external heating using visible and near infrared (NIR) light is demonstrated. By measuring the dependence of the RWGS reaction rates on the intensity and spectral power distribution of filtered light incident onto the nanostructured Pd@Nb 2O 5 catalyst, it is determined that the RWGS reaction is activated photothermally. That is the RWGS reaction is initiated by heat generated from thermalization of charge carriers in the Pd nanocrystals that are excited by interband and intraband absorption of visible and NIR light. Taking advantage of this photothermal effect, a visible and NIR responsive Pd@Nb 2O 5 hybrid catalyst that efficiently hydrogenates CO 2 to CO at an impressive rate as high as 1.8 mmol gcat –1 h –1 is developed. The mechanism of this photothermal reaction involves H 2 dissociation on Pd nanocrystals and subsequent spillover of H to the Nb 2O 5 nanorods whereupon adsorbed CO 2 is hydrogenated to CO. Here, this work represents a significant enhancement in our understanding of the underlying mechanism of photothermally driven CO 2 reduction and will help guide the way toward the development of highly efficient catalysts thatmore » exploit the full solar spectrum to convert gas-phase CO 2 to valuable chemicals and fuels.« less

Authors:
 [1];  [1];  [2];  [3];  [1];  [1];  [1];  [1];  [1];  [4];  [5];  [6];  [1];  [1];  [1];  [1]
  1. Univ. of Toronto, Toronto, ON (Canada)
  2. Soochow Univ., Jiangsu (China)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  4. Univ. Complutense de Madrid, Madrid (Spain)
  5. National Univ. of Singapore (Singapore)
  6. American Univ. of Beirut, Beirut (Lebanon)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1329168
Grant/Contract Number:
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Advanced Science
Additional Journal Information:
Journal Volume: 3; Journal Issue: 10; Journal ID: ISSN 2198-3844
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY

Citation Formats

Jia, Jia, O'Brien, Paul G., He, Le, Qiao, Qiao, Fei, Teng, Reyes, Laura M., Burrow, Timothy E., Dong, Yuchan, Liao, Kristine, Varela, Maria, Pennycook, Stephen J., Hmadeh, Mohamad, Helmy, Amr S., Kherani, Nazir P., Perovic, Doug D., and Ozin, Geoffrey A. Visible and near-infrared photothermal catalyzed hydrogenation of gaseous CO2 over nanostructured Pd@Nb2O5. United States: N. p., 2016. Web. doi:10.1002/advs.201600189.
Jia, Jia, O'Brien, Paul G., He, Le, Qiao, Qiao, Fei, Teng, Reyes, Laura M., Burrow, Timothy E., Dong, Yuchan, Liao, Kristine, Varela, Maria, Pennycook, Stephen J., Hmadeh, Mohamad, Helmy, Amr S., Kherani, Nazir P., Perovic, Doug D., & Ozin, Geoffrey A. Visible and near-infrared photothermal catalyzed hydrogenation of gaseous CO2 over nanostructured Pd@Nb2O5. United States. doi:10.1002/advs.201600189.
Jia, Jia, O'Brien, Paul G., He, Le, Qiao, Qiao, Fei, Teng, Reyes, Laura M., Burrow, Timothy E., Dong, Yuchan, Liao, Kristine, Varela, Maria, Pennycook, Stephen J., Hmadeh, Mohamad, Helmy, Amr S., Kherani, Nazir P., Perovic, Doug D., and Ozin, Geoffrey A. Tue . "Visible and near-infrared photothermal catalyzed hydrogenation of gaseous CO2 over nanostructured Pd@Nb2O5". United States. doi:10.1002/advs.201600189. https://www.osti.gov/servlets/purl/1329168.
@article{osti_1329168,
title = {Visible and near-infrared photothermal catalyzed hydrogenation of gaseous CO2 over nanostructured Pd@Nb2O5},
author = {Jia, Jia and O'Brien, Paul G. and He, Le and Qiao, Qiao and Fei, Teng and Reyes, Laura M. and Burrow, Timothy E. and Dong, Yuchan and Liao, Kristine and Varela, Maria and Pennycook, Stephen J. and Hmadeh, Mohamad and Helmy, Amr S. and Kherani, Nazir P. and Perovic, Doug D. and Ozin, Geoffrey A.},
abstractNote = {The reverse water gas shift (RWGS) reaction driven by Nb2O5 nanorod-supported Pd nanocrystals without external heating using visible and near infrared (NIR) light is demonstrated. By measuring the dependence of the RWGS reaction rates on the intensity and spectral power distribution of filtered light incident onto the nanostructured Pd@Nb2O5 catalyst, it is determined that the RWGS reaction is activated photothermally. That is the RWGS reaction is initiated by heat generated from thermalization of charge carriers in the Pd nanocrystals that are excited by interband and intraband absorption of visible and NIR light. Taking advantage of this photothermal effect, a visible and NIR responsive Pd@Nb2O5 hybrid catalyst that efficiently hydrogenates CO2 to CO at an impressive rate as high as 1.8 mmol gcat–1 h–1 is developed. The mechanism of this photothermal reaction involves H2 dissociation on Pd nanocrystals and subsequent spillover of H to the Nb2O5 nanorods whereupon adsorbed CO2 is hydrogenated to CO. Here, this work represents a significant enhancement in our understanding of the underlying mechanism of photothermally driven CO2 reduction and will help guide the way toward the development of highly efficient catalysts that exploit the full solar spectrum to convert gas-phase CO2 to valuable chemicals and fuels.},
doi = {10.1002/advs.201600189},
journal = {Advanced Science},
number = 10,
volume = 3,
place = {United States},
year = {Tue Jul 05 00:00:00 EDT 2016},
month = {Tue Jul 05 00:00:00 EDT 2016}
}

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Cited by: 7works
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  • Rh/Nb/sub 2/O/sub 5/ or Cu/SiO/sub 2/-Rh/Nb/sub 2/O/sub 5/ catalyst gives C/sub 2+/ hydrocarbons consisting mainly of C/sub 2/H/sub 6/ and C/sub 3/H/sub 8/ with 30-50% selectivity at temperatures ranging from 250 to 350/sup 0/C even at atmospheric pressure. Both the activity and the selectivity of the Cu/SiO/sub 2/-Rh/Nb/sub 2/O/sub 5/ catalyst, in which Cu/SiO/sub 2/ and Rh/Nb/sub 2/O/sub 5/, having different selectivities, are piled up in two layers, are significantly greater than those of Rh/Nb/sub 2/O/sub 5/ alone. In the Cu/SiO/sub 2/-Rh/Nb/sub 2/O/sub 5/ double-layer catalyst, Cu/SiO/sub 2/ is placed at the inlet of catalyst bed and is responsible formore » the conversion of CO/sub 2/ into CO at a significant magnitude. Some characteristic data of supported Rh catalysts relating to chemisorption of CO/sub 2/, CO, and H/sub 2/ were obtained by pulse-flow adsorption measurements. In order to speculate the reaction scheme, a relationship between the catalytic activity and the chemisorption data is discussed.« less
  • Solvent-refined lignite (SRL) can be produced by treating lignite (not dried) with CO-H/sub 2/, donor solvent and high temperature. This reactive black solid softens at about 150/sup 0/C, is soluble in many organic solvents, is very low in ash and sulfur, and appears to be a good feedstock for further upgrading. Thus, a wide-ranging study was undertaken to determine the best reducing conditions for converting SRL to light distillable liquid fuels and/or chemical feedstocks. Batch autoclave studies were carried out in the temperature range of 375-450/sup 0/C, hydrogen pressure range of 1500-4500 psi, with catalysts Ni-Mo-Al/sub 2/O/sub 3/, Co-Mo-Al/sub 2/O/submore » 3/, Ni-W-Al/sub 2/O/sub 3/. Ni-W-SiO/sub 2/-Al/sub 2/O/sub 3/, SiO/sub 2/-Al/sub 2/O/sub 3/, Al/sub 2/O/sub 3/,SnCl/sub 2/, and presulfided catalysts Ni-Mo-Al/sub 2/O/sub 3/, Co-Mo-Al/sub 2/O/sub 3/, Ni-W-Al/sub 2/O/sub 3/. Varying amounts of the solvents tetrahydrofuran, tetralin, napthalene, and FS-120 petroleum fraction were also studied. Reductions without any solvent were studied too and were quite successful. The results were evaluated in terms of the amount of light liquids produced, deoxygenation, denitrification, hydrogen-carbon ratios, aromatic-aliphatic hydrogen ratios, and benzene solubility of unconverted material. Best results were obtained with a presulfided Ni-Mo-Al/sub 2/O/sub 3/ catalyst at 450/sup 0/C, operating pressure of about 3500 psi with a 1:1 SRL-tetralin solvent ratio (90 percent overall conversion, approx.20 percent light liquid (1), 15 percent light oil (2), 20 percent heavy oil (3 and 4), 10 percent unconverted). However, operating without any solvent also gave satisfactory results (88 percent overall conversion, 40 percent light liquid, 10 percent light oil, 10 percent heavy oil, 12 percent unconverted. Detailed gas chromatography-mass spectrometry (GC-MS) studies of selected liquid fractions indicate a high degree of aromaticity as tetralins, hydrophenanthrenes, and hydropyrenes.« less
  • The aim of this paper is to report a new catalytic system that exhibits kinetic oscillations, namely the hydrogenation of acetylene in the presence of CO over Pt/Al[sub 2]O[sub 3] and Pd/Al[sub 2]O[sub 3]. Under present of CO over Pt/Al[sub 2]O[sub 3] and Pd/Al[sub 2]O[sub 3]. Under present conditions, CO does not take part in any reaction. Despite this, CO probably plays a significant role for the oscillations. Earlier experiments have shown that strongly adsorbed CO can be displaced by acetylene. A periodic change in the CO coverage on the surface is therefore not unlikely. 20 refs., 4 figs., 1more » tab.« less
  • The complex gaseous niobium oxide molecules Nb/sub 2/O/sub 4/, Nb/sub 2/O/sub 5/, Nb/sub 4/O/sub 9/, and Nb/sub 4/O/sub 10/ were identified for the first time in a Knudsen cell-mass spectrometric study of the vapors in equilibrium over a condensed phase resulting from extensive vaporization of lithium niobate with lithium depletion. These molecules were characterized thermochemically from the study of several all-gas equilibria. The resulting atomization energies are ..delta..H/sup 0//sub 0,at/(Nb/sub 2/O/sub 4/) = 3322 +- 45 kJ mol/sup -1/; ..delta..H/sup 0//sub 0,at/(Nb/sub 2/O/sub 5/) = 3910 +- 59 kJ mol/sup -1/; ..delta..H/sup 0//sub 0,at/(Nb/sub 4/O/sub 9/) = 7958 +- 82more » kJ mol/sup -1/; ..delta..H/sup 0//sub 0,at/(Nb/sub 4/O/sub 10/) = 8595 +- 71 kJ mol/sup -1/. The corresponding standard heats of formation are ..delta..H/sup 0//sub f//sub ,298/(Nb/sub 2/O/sub 4/,g) = -909 +- 45 kJ mol/sup -1/; ..delta..H/sup 0//sub f//sub ,298/(Nb/sub 2/O/sub 5/,g) = -1252 +- 59 kJ mol/sup -1/; ..delta..H/sup 0//sub f//sub ,298/(Nb/sub 4/O/sub 9/,g) = -2889 +- 82 kJ mol/sup -1/; ..delta..H/sup 0//sub f//sub ,298/(Nb/sub 4/O/sub 10/,g) = -3281 +- 71 kJ mol/sup -1/.« less