ELECTROCHEMICAL MODIFICATION OF CH3OH OXIDATION SELECTIVITY AND ACTIVITY ON A PT SINGLE-PELLET CATALYTIC REACTOR

被引:91
作者
CAVALCA, CA
LARSEN, G
VAYENAS, CG
HALLER, GL
机构
[1] YALE UNIV,MASON LAB,DEPT CHEM ENGN,NEW HAVEN,CT 06520
[2] UNIV PATRAS,DEPT CHEM ENGN,INST CHEM ENGN & HIGH TEMP CHEM PROC,GR-26110 PATRAI,GREECE
关键词
D O I
10.1021/j100125a005
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
It was found that the catalytic activity and selectivity of Pt for the oxidation of methanol to formaldehyde and CO2 can be altered significantly and reversibly by depositing a Pt catalyst film on an yttria-stabilized zirconia (YSZ) disc and by applying current or potential between the catalyst film and a Ag film deposited on the other side of the O2--conducting YSZ disc. Both the catalyst film and the Ag counter and reference electrodes are exposed to the reacting CH3OH-O2 mixture. The observed increase in the rate of H2CO production was typically a factor of 100 higher than the rate of O2- supply to the catalyst with a concomitant 2-fold increase in selectivity. This demonstration of the effect of non-Faradaic electrochemical modification of catalytic activity (NEMCA) to reversibly modify catalyst activity and selectivity in a single-pellet flow reactor is a new result. It has considerable practical importance as it shows that the NEMCA effect can be utilized in conventional flow-type catalytic reactors. The present study has also shown the spontaneous generation of significant reaction-driven potential differences between the catalyst and the counter electrode. This observation is significant both for catalytic and also for sensor applications.
引用
收藏
页码:6115 / 6119
页数:5
相关论文
共 22 条
[1]   THE EFFECTS OF STRUCTURED OVERLAYERS OF SULFUR ON THE KINETICS AND MECHANISM OF SIMPLE REACTIONS ON PT(111) .1. FORMALDEHYDE DECOMPOSITION [J].
ABBAS, NM ;
MADIX, RJ .
APPLICATIONS OF SURFACE SCIENCE, 1981, 7 (03) :241-275
[2]   ELECTROCATALYTIC DECOMPOSITION OF HYDROGEN-SULFIDE [J].
ALQAHTANY, H ;
CHIANG, PH ;
ENG, D ;
STOUKIDES, M ;
ROBBAT, A .
CATALYSIS LETTERS, 1992, 13 (03) :289-295
[3]   SURFACE STUDY OF A AG ELECTRODE ON A SOLID ELECTROLYTE USED AS OXYGEN SENSOR [J].
ARAKAWA, T ;
SAITO, A ;
SHIOKAWA, J .
APPLICATIONS OF SURFACE SCIENCE, 1983, 16 (3-4) :365-372
[4]   NON-FARADAIC ELECTROCHEMICAL MODIFICATION OF CATALYTIC ACTIVITY .1. THE CASE OF ETHYLENE OXIDATION ON PT [J].
BEBELIS, S ;
VAYENAS, CG .
JOURNAL OF CATALYSIS, 1989, 118 (01) :125-146
[5]  
BEBELIS S, 1992, J CATAL, V137, P278
[6]   COMPARISONS BETWEEN COVERAGE-DEPENDENT INFRARED FREQUENCIES FOR CARBON-MONOXIDE ADSORBED ON ORDERED PT(111), PT(100), AND PT(110) IN ELECTROCHEMICAL AND ULTRAHIGH-VACUUM ENVIRONMENTS [J].
CHANG, SC ;
LEUNG, LWH ;
WEAVER, MJ .
JOURNAL OF PHYSICAL CHEMISTRY, 1989, 93 (14) :5341-5345
[7]   ELECTROCATALYTIC METHANE DIMERIZATION WITH A YB-DOPED SRCEO3 SOLID ELECTROLYTE [J].
CHIANG, PH ;
ENG, D ;
STOUKIDES, M .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1991, 138 (06) :L11-L12
[8]   A COMPARISON OF ELECTROCHEMICAL AND GAS-PHASE DECOMPOSITION OF METHANOL ON PLATINUM SURFACES [J].
FRANASZCZUK, K ;
HERRERO, E ;
ZELENAY, P ;
WIECKOWSKI, A ;
WANG, J ;
MASEL, RI .
JOURNAL OF PHYSICAL CHEMISTRY, 1992, 96 (21) :8509-8516
[9]   WORK FUNCTION MEASUREMENTS ON CATALYST FILMS SUBJECT TO INSITU ELECTROCHEMICAL PROMOTION [J].
LADAS, S ;
BEBELIS, S ;
VAYENAS, CG .
SURFACE SCIENCE, 1991, 251 :1062-1068
[10]   KINETICS AND REACTION PATHWAYS OF METHANOL OXIDATION ON PLATINUM [J].
MCCABE, RW ;
MCCREADY, DF .
JOURNAL OF PHYSICAL CHEMISTRY, 1986, 90 (07) :1428-1435