New Insights into the Synthesis of Methanol on Copper

2013 Spring Symposium

Charles H.F. Peden1, Charles A. Mims2, Yong Yang1,3, Dong­hai Mei1, Charles T. Camp­bell3
1 Insti­tute for Inte­grat­ed Catal­y­sis, Pacif­ic North­west Nation­al Lab­o­ra­to­ry,
P.O. Box 999, Rich­land, WA 99354 USA
2 Depart­ment of Chem­i­cal Engi­neer­ing and Applied Chem­istry
Uni­ver­si­ty of Toron­to, Toron­to ON M5S3E5 Cana­da
3 Depart­ment of Chem­istry Uni­ver­si­ty of Wash­ing­ton, Seat­tle WA 98195 USA

Abstract — The mech­a­nism of methanol syn­the­sis on cop­per-based cat­a­lysts has been exten­sive­ly stud­ied and remains a tar­get of research because of the sig­nif­i­cance of this reac­tion in the chem­i­cal indus­try and methanol’s poten­tial as a liq­uid energy/hydrogen car­ri­er. A recent DFT and micro­ki­net­ic mod­el­ing study by Grabow and Mavrikakis [1] con­tains a thor­ough review of the cur­rent state of our under­stand­ing of this reac­tion. These recent mod­els allow for con­ver­sion of both CO (by direct hydro­gena­tion) and CO2 (via for­mate inter­me­di­ates) to methanol. Although trac­er exper­i­ments have shown that CO2 is the pre­ferred reac­tant over CO in H2:CO:CO2 mix­tures under com­mer­cial con­di­tions, the rel­a­tive impor­tance of these chan­nels under var­i­ous con­di­tions is still uncer­tain [1]. Fur­ther­more, the role of water in the reac­tion mech­a­nism has received lit­tle atten­tion, despite long estab­lished effects of water and CO2 in the con­ver­sions of syn­gas [2]. Our recent DFT study has point­ed out that water can have sig­nif­i­cant effects in methanol syn­the­sis and that a sep­a­rate methanol for­ma­tion mech­a­nism via a car­boxyl inter­me­di­ate is ener­get­i­cal­ly pos­si­ble [3]. In this pre­sen­ta­tion, we describe par­tic­u­lar­ly strong effects of water on the con­ver­sion of both CO and CO2 at tem­per­a­tures below those of com­mer­cial prac­tice, and sup­port for an inter­me­di­ate com­mon to both CO and CO2 [4].
1. Grabow, LC; Mavrikakis, M ACS Catal. 1 (2011) 365.
2. Para­meswaran, VR; Lee, S; Wen­der; I Fuel Sci­ence Techn. Intl. 7 (1989) 899.
3. Zhao, Y-F; Yang, Y; Mims, CA.; Peden, CHF; Li, J; Mei, D J. Catal. 281 (2011) 199.
4. Yang, Y; Mims, CA.; Mei, DH; Peden, CHF; Camp­bell, CT J. Catal. 298 (2012) 10

Charles H.F. Peden

Charles H.F. Peden

Biog­ra­phy — Chuck Peden is Asso­ciate Direc­tor of the Insti­tute for Inte­grat­ed Catal­y­sis at Pacif­ic North­west Nation­al Lab­o­ra­to­ry (PNNL). He is also a Lab­o­ra­to­ry Fel­low, and man­ages and par­tic­i­pates in mul­ti­ple tech­ni­cal projects with­in the Phys­i­cal Sci­ences Divi­sion at PNNL. He joined PNNL in 1992 fol­low­ing a nine-year tenure at San­dia Nation­al Lab­o­ra­to­ries in Albu­querque, New Mex­i­co, as a Senior Mem­ber of the tech­ni­cal Staff in the Inor­gan­ic Mate­ri­als Chem­istry Depart­ment. Peden’s main research inter­ests are in the sur­face and inter­fa­cial chem­istry of inor­gan­ic solids; in par­tic­u­lar, the het­ero­ge­neous cat­alyt­ic chem­istry of met­als and oxides with an empha­sis on reac­tion mech­a­nisms and mate­ri­als structure/function rela­tion­ships. He is best known as a leader in the devel­op­ment of the mech­a­nisms of auto­mo­bile exhaust cat­alyt­ic reac­tions. After grad­u­at­ing with dis­tinc­tion from Cal­i­for­nia State Uni­ver­si­ty, Chico with a B.S. in chem­istry, Peden com­plet­ed his Ph.D. in phys­i­cal chem­istry at the Uni­ver­si­ty of Cal­i­for­nia, San­ta Bar­bara under the direc­tion of Ralph G. Pear­son. He then spent two years as a post­doc­tor­al asso­ciate with D. Wayne Good­man at San­dia Nation­al Lab­o­ra­to­ries in Albu­querque, New Mex­i­co before join­ing the sci­en­tif­ic staff there. Peden has writ­ten or con­tributed to more than 235 peer-reviewed pub­li­ca­tions (H-fac­tor > 40) and 3 issued U.S. patents on top­ics such as auto­mo­bile exhaust catal­y­sis, hydro­car­bon reform­ing on bimetal­lic cat­a­lysts, the struc­ture of hydropro­cess­ing cat­a­lysts, the syn­the­sis and char­ac­ter­i­za­tion of nov­el sup­port­ed sol­id acid cat­a­lysts, and the struc­ture and chem­istry of oxide sur­faces. He is a mem­ber of the Amer­i­can Chem­i­cal Soci­ety, the Amer­i­can Insti­tute of Chem­i­cal Engi­neers, the Soci­ety of Auto­mo­tive Engi­neers, and the North Amer­i­can Catal­y­sis Soci­ety. Peden was elect­ed a Fel­low of the Amer­i­can Vac­u­um Soci­ety in 2000, and the Amer­i­can Asso­ci­a­tion for the Advance­ment of Sci­ence in 2009 and the Amer­i­can Chem­i­cal Soci­ety in 2012. He cur­rent­ly serves as Past-Chair of the ACS Catal­y­sis Sci­ence and Tech­nol­o­gy (CATL) Divi­sion.