TY - JOUR
T1 - Selective catalytic reduction at quasi-perfect Pt(100) domains
T2 - A universal low-temperature pathway from nitrite to N
2
AU - Duca, Matteo
AU - Figueiredo, Marta C.
AU - Climent, Victor
AU - Rodriguez, Paramaconi
AU - Feliu, Juan M.
AU - Koper, Marc T M
AU - Rodriguez, Paramaconi
PY - 2011/7/20
Y1 - 2011/7/20
N2 - The highly selective conversion of nitrite to N
2 at a quasi-perfect Pt(100) electrode in alkaline media was investigated with a particular emphasis on its structure sensitivity and its mechanism. High-quality (100) terraces are required to optimize the catalytic activity and steer the selectivity to N
2: defects of any symmetry dramatically reduce the N
2 evolution at [(100) × (110)] and [(100) × (111)] surfaces. On the other hand, nitrite reduction proves to be an additional example of the unique intrinsic ability of (100) surfaces to catalyze reactions involving bond breaking and successive bond formation. In the present case, (100) is able to reduce nitrite to NH
2,ads, which in a certain potential window combines with NO
ads to give N
2 in a Langmuir-Hinshelwood reaction. Our findings are similar to those for other processes generating N
2, from bacterial anoxic ammonia oxidation ("anammox") to the high-temperature NO + NH
3 reaction at Pt(100) crystals under ultra-high-vacuum conditions, thus suggesting that the combination of these two nitrogen-containing species is a universal (low-temperature) pathway to N
2. The advantages of this pathway over other N
2-generating pathways are pointed out.
AB - The highly selective conversion of nitrite to N
2 at a quasi-perfect Pt(100) electrode in alkaline media was investigated with a particular emphasis on its structure sensitivity and its mechanism. High-quality (100) terraces are required to optimize the catalytic activity and steer the selectivity to N
2: defects of any symmetry dramatically reduce the N
2 evolution at [(100) × (110)] and [(100) × (111)] surfaces. On the other hand, nitrite reduction proves to be an additional example of the unique intrinsic ability of (100) surfaces to catalyze reactions involving bond breaking and successive bond formation. In the present case, (100) is able to reduce nitrite to NH
2,ads, which in a certain potential window combines with NO
ads to give N
2 in a Langmuir-Hinshelwood reaction. Our findings are similar to those for other processes generating N
2, from bacterial anoxic ammonia oxidation ("anammox") to the high-temperature NO + NH
3 reaction at Pt(100) crystals under ultra-high-vacuum conditions, thus suggesting that the combination of these two nitrogen-containing species is a universal (low-temperature) pathway to N
2. The advantages of this pathway over other N
2-generating pathways are pointed out.
UR - http://www.scopus.com/inward/record.url?scp=79960217383&partnerID=8YFLogxK
U2 - 10.1021/ja203234v
DO - 10.1021/ja203234v
M3 - Article
AN - SCOPUS:79960217383
SN - 0002-7863
VL - 133
SP - 10928
EP - 10939
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 28
ER -