Hydrogen spillover on Ni–CsxH3−xPW12O40 (x = 0, 1, 2) double-function hydrocracking catalyst was studied by temperature-programmed desorption (H2-TPD and NH3/H2-TPD) and thermodynamic calculations. The results of H2-TPD show that the hydrogen adsorption amount on the two-component Ni–CsxH3−xPW12O40 (x = 0, 1, 2) catalysts is much greater than that on single-component catalysts, such as nickel, tungstophosphoric acid and its cesium salts. Moreover, the H+ content is related to the content of Ni–CsxH3−xPW12O40. The above phenomena can be explained by the spillover hydrogen H combining with H+ to form Hn+ (n = 2, 3). The results of NH3/H2-TPD can also indirectly prove the existence of Hn+. It is demonstrated by the theoretical calculation that the formation of Hn+ (n = 2, 3) from H and H+ is favorable in energy, and NH3 may combine with H3+ to form NH6+.
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