A novel room-temperature solid-state reaction is developed to synthesize cotton-like CoB alloy (CoBssR) catalysts with a large specific surface area of 222.4 m(2) g(-1). In the hydrolysis of ammonia borane catalyzed by the CoBssR, the rate of hydrogen generation can reach 68.7 mL min(-1) with a turnover frequency (TOF) value of ca. 6.9 L-hydrogen min(-1)g(-1) at 25 degrees C. The TOF value is about 2 times as large as that of CoB alloy prepared by a regular solid-state reaction, which is also much higher than those of the CoB catalysts recently reported in the literature. The activation energy of the hydrolysis of ammonia borane catalyzed by the CoBssR is as low as 22.78 kJ mol(-1), hinting that the CoBssR possesses high catalytic activity, which may be attributed to the large specific surface area and the abundant porous structure. The high catalytic performance, good recoverability and low cost of the CoBssR enable it to be a promissing catalyst condidate in the hydrolysis of ammonia borane for hydrogen production in commercial application. (C) 2016 Elsevier Inc. All rights reserved.