Finding efficient photocatalysts is the key to achieve sustainable hydrogen production. In this work, a rational design of Cd2+ doped Zn3In2S6 (ZIS) and constructed heterojunction structure with g-C3N4 (GCN) to form GCN/Cd/ZIS composite was carried out. The synergistic effect of Cd2+ doping and heterojunction construction in the photocatalytic hydrogen production process was probed. The results showed that doping Cd2+ modified the bandgap structure of ZIS and improved the photocatalytic activity. The heterojunction construction between Cd/ZIS and GCN also effectively promoted the separation and migration of photogenerated carriers, which significantly improved the hydrogen production performance of GCN/Cd/ZIS composite. The hydrogen production rate of 15% Cd/ZIS and 5% GCN/Cd/ZIS was 2.45 mmol·g-1·h-1, 3.34 mmol·g-1·h-1, which was 4.3 and 5.9 times higher than that of ZIS (0.57 mmol·g-1·h-1), respectively. This study provides strong evidence that doping and heterojunction construction can synergistically improve the photocatalytic activity.

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