Boron-based metal-free catalysts for oxidative dehydrogenation of propane (ODHP) have drawn great attention in both academia and industry due to their impressive activity and olefin selectivity. Herein

the SiO

2

and B

2

O

3

sequentially coated honeycomb cordierite catalyst is designed by a two-step wash-coat method with different B

2

O

3

loadings (0.1%-10%) and calcination temperatures (600

700

800 ℃). SiO

2

obtained by TEOS hydrolysis acts as a media layer to bridge the cordierite substrate and boron oxide

via

abundant Si-OH groups. The welldeveloped straight channels of honeycomb cordierite make it possible to carry out the reactor under high gas hourly space velocity (GHSV) and the thin wash-coated B

2

O

3

layer can effectively facilitate the pore diffusion on the catalyst. The prepared B

2

O

3

/SiO

2

@HC monolithic catalyst exhibits good catalytic performance at low boron oxide loading and achieves excellent propylene selectivity (86.0%)

olefin selectivity (97.6%

propylene and ethylene) and negligible CO

2

(0.1%) at 16.9% propane conversion under high GHSV of 345

600 ml·(g B

2

O

3

)

-1

·h

-1

leading to a high propylene space time yield of 15.7 g C

3

H

6

·(g B

2

O

3

)

-1

·h

-1

by suppressing the overoxidation. The obtained results strongly indicate that the boron-based monolithic catalyst can be properly fabricated to warrant the high activity and high throughput with its high gas/surface ratio and straight channels.