Glycerol steam reforming (GSR) is one of the promising technologies that can realize renewable hydrogen production and efficient utilization of crude glycerol. To illuminate the functions of Ca content (3%

6%

9%

and 12%

by mass) and preparation method for Ni/ATP catalyst structure and its catalytic behaviors

the Ni-

x

Ca/ATP (

x

?=?3%

6%

9%

and 12%

by mass) catalysts are prepared by co-impregnation (

ci

) and hydrothermal synthesis (

hs

) method and then tested in GSR. Characterization results of XRD

N

2

adsorption–desorption

H

2

-TPR

HRTEM

XPS

and NH

3

/CO

2

-TPD demonstrate that the combined effect between appropriate Ca additive (6%

by mass) and

hs

enhance catalyst reducibility

uniform distribution of Ca additive and nickel species over ATP

and adsorption for CO

2

. This attributes to

hs

method protects the ATP framework through suppressing the interaction of Ca with ATP and promotes the formation of Ni-CaO interface sites. Therefore

Ni-6Ca/ATP-

hs

exhibits the highest conversion (86.77%) of glycerol to gas product and H

2

yield (76.17%) and selectivity (58.56%) during GSR. Furthermore

XRD

HRTEM

TG-DTG and Raman analyses confirm that Ni-6Ca/ATP-

hs

also reveals outstanding anti-sintering and coke resistance. In addition

the structural evolution process of Ni/ATP catalyst with Ca introduction and

hs

method is presented. Considering the high performance

simple preparation process and low cost

the as-prepared catalyst providing new opportunities for utilization of glycerol derived from biodiesel industry.