Liquid-phase hydrodeoxygenation of lignin-derived phenolics on Pd/Fe: A mechanistic study

Zhang, Jianghao; Sun, Junming; Sudduth, Berlin; Pereira Hernandez, Xavier; Wang, Yong

doi:10.1016/j.cattod.2018.12.027

Liquid-phase hydrodeoxygenation of lignin-derived phenolics on Pd/Fe: A mechanistic study

Journal Article · Wed Dec 12 00:00:00 EST 2018 · Catalysis Today

DOI:https://doi.org/10.1016/j.cattod.2018.12.027· OSTI ID:1490379

Zhang, Jianghao ^[1]; ^[1]; Sudduth, Berlin ^[1]; ^[1]; Wang, Yong ^[2]

Washington State Univ., Pullman, WA (United States). Gene & Linda Voiland School of Chemical Engineering and Bioengineering
Washington State Univ., Pullman, WA (United States). Gene & Linda Voiland School of Chemical Engineering and Bioengineering; Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Inst. for Integrated Catalysis

Although Pd/Fe bimetallic catalysts have been extensively studied in vapor-phase hydrodeoxygenation of phenolics (i.e., guaiacol, cresol), little is yet known about their performance in liquid-phase reactions. In this work, we present a mechanistic study on the Pd/Fe bimetallic catalysts in liquid-phase hydrodeoxygenation of phenolics. The role of tautomerization in hydrodeoxygenation of the lignin-derived phenolics, particularly for ring saturation, is systematically studied by employing two representative modeling compounds: phenol (a molecule that is keto-enol tautomeric) and diphenyl ether (a molecule that does not allow ketol-enol tautomerization). It was found that although the addition of oxyphilic Fe inhibits the direct aromatic ring saturation reaction typically occurring on Pd, tautomerization opens another reaction pathway toward ring saturation products (i.e. cyclohexanone, cyclohexanol, cyclohexane et al.), where both tautomerization and the hydrogenation of keto isomers are significantly enhanced to produce cyclohexanol followed by direct hydrogenolysis of the cyclohexanol to cyclohexane.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC05-76RL01830; FG02-05ER15712

OSTI ID:: 1490379

Alternate ID(s):: OSTI ID: 1636640

Journal Information:: Catalysis Today, Journal Name: Catalysis Today Vol. 339; ISSN 0920-5861

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (67)

Raman microspectroscopy of some iron oxides and oxyhydroxides de Faria, D. L. A.; Venâncio Silva, S.; de Oliveira, M. T. Journal of Raman Spectroscopy, Vol. 28, Issue 11 https://doi.org/10.1002/(SICI)1097-4555(199711)28:11<873::AID-JRS177>3.0.CO;2-B	journal	November 1997
A Route for Lignin and Bio-Oil Conversion: Dehydroxylation of Phenols into Arenes by Catalytic Tandem Reactions Wang, Xingyu; Rinaldi, Roberto Angewandte Chemie International Edition, Vol. 52, Issue 44 https://doi.org/10.1002/anie.201304776	journal	September 2013
Iron(II) Disulfides as Precursors of Highly Selective Catalysts for Hydrodeoxygenation of Dibenzyl Ether into Toluene Ji, Na; Wang, Xingyu; Weidenthaler, Claudia ChemCatChem, Vol. 7, Issue 6 https://doi.org/10.1002/cctc.201500041	journal	February 2015
On the mechanism of hydrodeoxygenation of ortho substituted phenols Furimsky, E.; Mikhlin, J. A.; Jones, D. Q. The Canadian Journal of Chemical Engineering, Vol. 64, Issue 6 https://doi.org/10.1002/cjce.5450640615	journal	December 1986
Solvent Effects on the Hydrogenolysis of Diphenyl Ether with Raney Nickel and their Implications for the Conversion of Lignin Wang, Xingyu; Rinaldi, Roberto ChemSusChem, Vol. 5, Issue 8, p. 1455-1466 https://doi.org/10.1002/cssc.201200040	journal	April 2012
Guaiacol Hydrodeoxygenation Mechanism on Pt(111): Insights from Density Functional Theory and Linear Free Energy Relations Lee, Kyungtae; Gu, Geun Ho; Mullen, Charles A. ChemSusChem, Vol. 8, Issue 2 https://doi.org/10.1002/cssc.201402940	journal	December 2014
Catalytic Total Hydrodeoxygenation of Biomass-Derived Polyfunctionalized Substrates to Alkanes Nakagawa, Yoshinao; Liu, Sibao; Tamura, Masazumi ChemSusChem, Vol. 8, Issue 7 https://doi.org/10.1002/cssc.201403330	journal	February 2015
Pd/Nb ₂ O ₅ /SiO ₂ Catalyst for the Direct Hydrodeoxygenation of Biomass-Related Compounds to Liquid Alkanes under Mild Conditions Shao, Yi; Xia, Qineng; Liu, Xiaohui ChemSusChem, Vol. 8, Issue 10 https://doi.org/10.1002/cssc.201500053	journal	April 2015
Hydrodeoxygenation of Lignin-derived Diaryl Ethers to Aromatics and Alkanes Using Nickel on Zr-doped Niobium Phosphate Jin, Shaohua; Chen, Xiao; Li, Chuang ChemistrySelect, Vol. 1, Issue 15 https://doi.org/10.1002/slct.201601107	journal	September 2016
Selective cleavage of C O bond in benzyl phenyl ether to aromatics over Pd–Fe bimetallic catalyst supported on ordered mesoporous carbon Kim, Jeong Kwon; Lee, Jong Kwon; Kang, Ki Hyuk Applied Catalysis A: General, Vol. 498 https://doi.org/10.1016/j.apcata.2015.03.034	journal	June 2015
Mo2C catalyzed vapor phase hydrodeoxygenation of lignin-derived phenolic compound mixtures to aromatics under ambient pressure Chen, Cha-Jung; Lee, Wen-Sheng; Bhan, Aditya Applied Catalysis A: General, Vol. 510 https://doi.org/10.1016/j.apcata.2015.10.043	journal	January 2016
Ni-based sol–gel catalysts as promising systems for crude bio-oil upgrading: Guaiacol hydrodeoxygenation study Bykova, M. V.; Ermakov, D. Yu.; Kaichev, V. V. Applied Catalysis B: Environmental, Vol. 113-114 https://doi.org/10.1016/j.apcatb.2011.11.051	journal	February 2012
Gas-phase hydrodeoxygenation of guaiacol over Fe/SiO2 catalyst Olcese, R. N.; Bettahar, M.; Petitjean, D. Applied Catalysis B: Environmental, Vol. 115-116 https://doi.org/10.1016/j.apcatb.2011.12.005	journal	April 2012
Effect of metal–support interaction on the selective hydrodeoxygenation of anisole to aromatics over Ni-based catalysts Yang, Yongxing; Ochoa-Hernández, Cristina; de la Peña O'Shea, Víctor A. Applied Catalysis B: Environmental, Vol. 145 https://doi.org/10.1016/j.apcatb.2013.03.038	journal	February 2014
Guaiacol derivatives and inhibiting species adsorption over MoS2 and CoMoS catalysts under HDO conditions: A DFT study Badawi, Michael; Paul, Jean-François; Cristol, Sylvain Catalysis Communications, Vol. 12, Issue 10 https://doi.org/10.1016/j.catcom.2011.02.010	journal	May 2011
Hydrodeoxygenation of mono- and dimeric lignin model compounds on noble metal catalysts Güvenatam, Burcu; Kurşun, Osman; Heeres, Erik H. J. Catalysis Today, Vol. 233 https://doi.org/10.1016/j.cattod.2013.12.011	journal	September 2014
Catalytic hydrodeoxygenation of anisole as lignin model compound over supported nickel catalysts Jin, Shaohua; Xiao, Zihui; Li, Chuang Catalysis Today, Vol. 234 https://doi.org/10.1016/j.cattod.2014.02.014	journal	October 2014
Amorphous unsupported Ni–Mo sulfide prepared by one step hydrothermal method for phenol hydrodeoxygenation Yoosuk, Boonyawan; Tumnantong, Dusadee; Prasassarakich, Pattarapan Fuel, Vol. 91, Issue 1 https://doi.org/10.1016/j.fuel.2011.08.001	journal	January 2012
Hydrodeoxygenation of lignin-derived phenolic compounds over bi-functional Ru/H-Beta under mild conditions Yao, Gang; Wu, Guangjun; Dai, Weili Fuel, Vol. 150 https://doi.org/10.1016/j.fuel.2015.02.035	journal	June 2015
Aqueous-phase hydrodeoxygenation of bio-derived phenols to cycloalkanes Zhao, Chen; He, Jiayue; Lemonidou, Angeliki A. Journal of Catalysis, Vol. 280, Issue 1 https://doi.org/10.1016/j.jcat.2011.02.001	journal	May 2011
Carbon-supported bimetallic Pd–Fe catalysts for vapor-phase hydrodeoxygenation of guaiacol Sun, Junming; Karim, Ayman M.; Zhang, He Journal of Catalysis, Vol. 306 https://doi.org/10.1016/j.jcat.2013.05.020	journal	October 2013
Highly selective bimetallic FeMoP catalyst for C–O bond cleavage of aryl ethers Rensel, Dallas J.; Rouvimov, Sergei; Gin, Megan E. Journal of Catalysis, Vol. 305 https://doi.org/10.1016/j.jcat.2013.05.026	journal	September 2013
Mechanisms of selective cleavage of C–O bonds in di-aryl ethers in aqueous phase He, Jiayue; Zhao, Chen; Mei, Donghai Journal of Catalysis, Vol. 309 https://doi.org/10.1016/j.jcat.2013.09.012	journal	January 2014
Kinetics and mechanism of m-cresol hydrodeoxygenation on a Pt/SiO2 catalyst Nie, Lei; Resasco, Daniel E. Journal of Catalysis, Vol. 317 https://doi.org/10.1016/j.jcat.2014.05.024	journal	August 2014
Selective vapor-phase hydrodeoxygenation of anisole to benzene on molybdenum carbide catalysts Lee, Wen-Sheng; Wang, Zhenshu; Wu, Ryan J. Journal of Catalysis, Vol. 319 https://doi.org/10.1016/j.jcat.2014.07.025	journal	November 2014
Reactivity and stability investigation of supported molybdenum oxide catalysts for the hydrodeoxygenation (HDO) of m-cresol Shetty, Manish; Murugappan, Karthick; Prasomsri, Teerawit Journal of Catalysis, Vol. 331 https://doi.org/10.1016/j.jcat.2015.07.034	journal	November 2015
Synthesis and hydrodeoxygenation activity of Ni2P/C – Effect of the palladium salt on lowering the nickel phosphide synthesis temperature Feitosa, Leon F.; Berhault, Gilles; Laurenti, Dorothée Journal of Catalysis, Vol. 340 https://doi.org/10.1016/j.jcat.2016.05.016	journal	August 2016
The use of bimetallics to control the selectivity for the upgrading of lignin-derived oxygenates: Reaction of anisole on Pt and PtZn catalysts Shi, Daming; Arroyo-Ramírez, Lisandra; Vohs, John M. Journal of Catalysis, Vol. 340 https://doi.org/10.1016/j.jcat.2016.05.020	journal	August 2016
Titania-supported gold-based nanoparticles efficiently catalyze the hydrodeoxygenation of guaiacol Nguyen, Thanh-Son; Laurenti, Dorothée; Afanasiev, Pavel Journal of Catalysis, Vol. 344 https://doi.org/10.1016/j.jcat.2016.09.016	journal	December 2016
High-pressure vapor-phase hydrodeoxygenation of lignin-derived oxygenates to hydrocarbons by a PtMo bimetallic catalyst: Product selectivity, reaction pathway, and structural characterization Yohe, Sara L.; Choudhari, Harshavardhan J.; Mehta, Dhairya D. Journal of Catalysis, Vol. 344 https://doi.org/10.1016/j.jcat.2016.10.009	journal	December 2016
Mechanistic analysis of the role of metal oxophilicity in the hydrodeoxygenation of anisole Tan, Qiaohua; Wang, Gonghua; Long, Alex Journal of Catalysis, Vol. 347 https://doi.org/10.1016/j.jcat.2017.01.008	journal	March 2017
Selective extraction and conversion of lignin in actual biomass to monophenols: A review Jiang, Zhicheng; Hu, Changwei Journal of Energy Chemistry, Vol. 25, Issue 6 https://doi.org/10.1016/j.jechem.2016.10.008	journal	November 2016
MgFe hydrotalcites-derived layered structure iron molybdenum sulfide catalysts for eugenol hydrodeoxygenation to produce phenolic chemicals Diao, Xinyong; Ji, Na; Zheng, Mingyuan Journal of Energy Chemistry, Vol. 27, Issue 2 https://doi.org/10.1016/j.jechem.2017.07.008	journal	March 2018
Selective conversion of m-cresol to toluene over bimetallic Ni–Fe catalysts Nie, Lei; de Souza, Priscilla M.; Noronha, Fabio B. Journal of Molecular Catalysis A: Chemical, Vol. 388-389 https://doi.org/10.1016/j.molcata.2013.09.029	journal	July 2014
Fast pyrolysis characteristics of lignocellulosic biomass with varying reaction conditions Choi, Hang Seok; Choi, Yeon Seok; Park, Hoon Chae Renewable Energy, Vol. 42 https://doi.org/10.1016/j.renene.2011.08.049	journal	June 2012
Adsorption of guaiacol on Fe (110) and Pd (111) from first principles Hensley, Alyssa J. R.; Wang, Yong; McEwen, Jean-Sabin Surface Science, Vol. 648 https://doi.org/10.1016/j.susc.2015.10.030	journal	June 2016
Effect of Zirconia Morphology on Hydrodeoxygenation of Phenol over Pd/ZrO ₂ de Souza, Priscilla M.; Rabelo-Neto, Raimundo C.; Borges, Luiz E. P. ACS Catalysis, Vol. 5, Issue 12 https://doi.org/10.1021/acscatal.5b01501	journal	November 2015
Experimental and Theoretical Insights into the Hydrogen-Efficient Direct Hydrodeoxygenation Mechanism of Phenol over Ru/TiO ₂ Nelson, Ryan C.; Baek, Byeongjin; Ruiz, Pamela ACS Catalysis, Vol. 5, Issue 11 https://doi.org/10.1021/acscatal.5b01554	journal	October 2015
Ordered Mesoporous Metal Carbides with Enhanced Anisole Hydrodeoxygenation Selectivity Lu, Qi; Chen, Cha-Jung; Luc, Wesley ACS Catalysis, Vol. 6, Issue 6 https://doi.org/10.1021/acscatal.6b00303	journal	May 2016
Mechanism of Dehydration of Phenols on Noble Metals via First-Principles Microkinetic Modeling Gu, Geun Ho; Mullen, Charles A.; Boateng, Akwasi A. ACS Catalysis, Vol. 6, Issue 5 https://doi.org/10.1021/acscatal.6b00776	journal	April 2016
Enhanced Hydrodeoxygenation of m -Cresol over Bimetallic Pt–Mo Catalysts through an Oxophilic Metal-Induced Tautomerization Pathway Robinson, Allison; Ferguson, Glen Allen; Gallagher, James R. ACS Catalysis, Vol. 6, Issue 7 https://doi.org/10.1021/acscatal.6b01131	journal	June 2016
Hydrodeoxygenation of Phenol over Pd Catalysts. Effect of Support on Reaction Mechanism and Catalyst Deactivation de Souza, Priscilla M.; Rabelo-Neto, Raimundo C.; Borges, Luiz E. P. ACS Catalysis, Vol. 7, Issue 3 https://doi.org/10.1021/acscatal.6b02022	journal	February 2017
Mechanistic Effects of Water on the Fe-Catalyzed Hydrodeoxygenation of Phenol. The Role of Brønsted Acid Sites Hensley, Alyssa J. R.; Wang, Yong; Mei, Donghai ACS Catalysis, Vol. 8, Issue 3 https://doi.org/10.1021/acscatal.7b02576	journal	January 2018
The Catalytic Valorization of Lignin for the Production of Renewable Chemicals Zakzeski, Joseph; Bruijnincx, Pieter C. A.; Jongerius, Anna L. Chemical Reviews, Vol. 110, Issue 6, p. 3552-3599 https://doi.org/10.1021/cr900354u	journal	June 2010
Screening of Catalysts for Hydrodeoxygenation of Phenol as a Model Compound for Bio-oil Mortensen, Peter M.; Grunwaldt, Jan-Dierk; Jensen, Peter A. ACS Catalysis, Vol. 3, Issue 8 https://doi.org/10.1021/cs400266e	journal	July 2013
Synergistic Catalysis between Pd and Fe in Gas Phase Hydrodeoxygenation of m -Cresol Hong, Yongchun; Zhang, He; Sun, Junming ACS Catalysis, Vol. 4, Issue 10 https://doi.org/10.1021/cs500578g	journal	August 2014
Hydrodeoxygenation of Guaiacol over Ru(0001): A DFT Study Chiu, Cheng-chau; Genest, Alexander; Borgna, Armando ACS Catalysis, Vol. 4, Issue 11 https://doi.org/10.1021/cs500911j	journal	October 2014
Phenol Deoxygenation Mechanisms on Fe(110) and Pd(111) Hensley, Alyssa J. R.; Wang, Yong; McEwen, Jean-Sabin ACS Catalysis, Vol. 5, Issue 2 https://doi.org/10.1021/cs501403w	journal	December 2014
Role of Dissociation of Phenol in Its Selective Hydrogenation on Pt(111) and Pd(111) Li, Gaofeng; Han, Jinyu; Wang, Hua ACS Catalysis, Vol. 5, Issue 3 https://doi.org/10.1021/cs501805y	journal	February 2015
Role of Keto Intermediates in the Hydrodeoxygenation of Phenol over Pd on Oxophilic Supports de Souza, Priscilla M.; Rabelo-Neto, Raimundo C.; Borges, Luiz E. P. ACS Catalysis, Vol. 5, Issue 2 https://doi.org/10.1021/cs501853t	journal	January 2015
Historical Developments in Hydroprocessing Bio-oils Elliott, Douglas C. Energy & Fuels, Vol. 21, Issue 3, p. 1792-1815 https://doi.org/10.1021/ef070044u	journal	May 2007
Anisole and Guaiacol Hydrodeoxygenation Reaction Pathways over Selected Catalysts Peters, Jonathan E.; Carpenter, John R.; Dayton, David C. Energy & Fuels, Vol. 29, Issue 2 https://doi.org/10.1021/ef502551p	journal	January 2015
Hydrodeoxygenation of 4-Methylphenol over Unsupported MoP, MoS ₂ , and MoO _x Catalysts ^† Whiffen, Victoria M. L.; Smith, Kevin J. Energy & Fuels, Vol. 24, Issue 9 https://doi.org/10.1021/ef901270h	journal	September 2010
Ni-Catalyzed Cleavage of Aryl Ethers in the Aqueous Phase He, Jiayue; Zhao, Chen; Lercher, Johannes A. Journal of the American Chemical Society, Vol. 134, Issue 51, p. 20768-20775 https://doi.org/10.1021/ja309915e	journal	December 2012
First-Principles Study of Phenol Hydrogenation on Pt and Ni Catalysts in Aqueous Phase Yoon, Yeohoon; Rousseau, Roger; Weber, Robert S. Journal of the American Chemical Society, Vol. 136, Issue 29 https://doi.org/10.1021/ja501592y	journal	July 2014
Gas-liquid equilibrium in hydrogen + n-hexadecane and methane + n-hexadecane at elevated temperatures and pressures Lin, Ho-Mu; Sebastian, Herbert M.; Chao, Kwang-Chu Journal of Chemical & Engineering Data, Vol. 25, Issue 3 https://doi.org/10.1021/je60086a012	journal	July 1980
Kinetics and Thermochemistry for the Gas-Phase Keto−Enol Tautomerism of Phenol ↔ 2,4-Cyclohexadienone Zhu, Li; Bozzelli, Joseph W. The Journal of Physical Chemistry A, Vol. 107, Issue 19 https://doi.org/10.1021/jp0212545	journal	May 2003
MoS2 monolayer catalyst doped with isolated Co atoms for the hydrodeoxygenation reaction Liu, Guoliang; Robertson, Alex W.; Li, Molly Meng-Jung Nature Chemistry, Vol. 9, Issue 8 https://doi.org/10.1038/nchem.2740	journal	March 2017
Selective production of arenes via direct lignin upgrading over a niobium-based catalyst Shao, Yi; Xia, Qineng; Dong, Lin Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms16104	journal	July 2017
Catalytic fast pyrolysis of lignocellulosic biomass Liu, Changjun; Wang, Huamin; Karim, Ayman M. Chem. Soc. Rev., Vol. 43, Issue 22 https://doi.org/10.1039/C3CS60414D	journal	January 2014
Rhodium-mediated hydrogenolysis/hydrolysis of the aryl ether bond in supercritical carbon dioxide/water: an experimental and theoretical approach Chatterjee, Maya; Chatterjee, Abhijit; Ishizaka, Takayuki Catalysis Science & Technology, Vol. 5, Issue 3 https://doi.org/10.1039/C4CY01417K	journal	January 2015
Insights into the catalytic activity and surface modification of MoO ₃ during the hydrodeoxygenation of lignin-derived model compounds into aromatic hydrocarbons under low hydrogen pressures Prasomsri, Teerawit; Shetty, Manish; Murugappan, Karthick Energy Environ. Sci., Vol. 7, Issue 8 https://doi.org/10.1039/C4EE00890A	journal	January 2014
Precise oxygen scission of lignin derived aryl ethers to quantitatively produce aromatic hydrocarbons in water Luo, Zhicheng; Wang, Yimeng; He, Mingyuan Green Chemistry, Vol. 18, Issue 2 https://doi.org/10.1039/C5GC01790D	journal	January 2016
Conversion of lignin model compounds under mild conditions in pseudo-homogeneous systems Chen, Lu; Xin, Jiayu; Ni, Lingli Green Chemistry, Vol. 18, Issue 8 https://doi.org/10.1039/C5GC03121D	journal	January 2016
Highly selective hydrodeoxygenation of anisole, phenol and guaiacol to benzene over nickel phosphide Li, Yunhua; Fu, Juan; Chen, Binghui RSC Advances, Vol. 7, Issue 25 https://doi.org/10.1039/C7RA00989E	journal	January 2017
Raman spectroscopy of iron oxides and (oxy)hydroxides at low laser power and possible applications in environmental magnetic studies Hanesch, Monika Geophysical Journal International, Vol. 177, Issue 3 https://doi.org/10.1111/j.1365-246X.2009.04122.x	journal	June 2009
Phase Modifiers Promote Efficient Production of Hydroxymethylfurfural from Fructose Roman-Leshkov, Yuriy; Chheda, Juben N.; Dumesic, James A. Science, Vol. 312, Issue 5782, p. 1933-1937 https://doi.org/10.1126/science.1126337	journal	June 2006

Cited By (1)

Recent advances in the selective catalytic hydrodeoxygenation of lignin-derived oxygenates to arenes Zhang, Jianghao; Sun, Junming; Wang, Yong Green Chemistry, Vol. 22, Issue 4 https://doi.org/10.1039/c9gc02762a	journal	January 2020

Similar Records

Carbon-supported bimetallic Pd–Fe catalysts for vapor-phase hydrodeoxygenation of guaiacol

Journal Article · Tue Oct 01 00:00:00 EDT 2013 · Journal of Catalysis · OSTI ID:1104622

Impact of solvent for individual steps of phenol hydrodeoxygenation with Pd/C and HZSM-5 as catalysts

Journal Article · Tue Dec 31 23:00:00 EST 2013 · Journal of Catalysis · OSTI ID:1234794

The synergistic effect between Ni sites and Ni-Fe alloy sites on hydrodeoxygenation of lignin-derived phenols

Journal Article · Sun Sep 15 00:00:00 EDT 2019 · Applied Catalysis B: Environmental · OSTI ID:1523385

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Liquid-phase hydrodeoxygenation
Pd/FeLignin-derived phenolics
Reaction mechanism
Tautomerization

Liquid-phase hydrodeoxygenation of lignin-derived phenolics on Pd/Fe: A mechanistic study

Citation Formats

References (67)

Cited By (1)

Similar Records

Related Subjects