CO₂ hydrogenation to value-added chemicals offers a promising route for alleviating the energy crisis and climate warming. Highly selective CO₂ hydrogenation is of great significance for reducing the costs of separation and circulation and improving production efficiency. However, it remains a great challenge due to the complex reaction network and co-existence of multiple active sites on catalysts. This review concentrates on the selectivity control in CO₂ hydrogenation to one-carbon (C1) products, including methanol, CO, and CH₄, which are the simplest CO₂ hydrogenation products and basic chemical building blocks. Based on the development of different catalyst systems, we here discuss multi-factors that affect CO₂ hydrogenation selectivity, including reaction conditions, such as temperature and pressure, and catalyst properties, such as active metal, metal dispersion, support, and promoter. We conclude the review by summarizing general rules for manipulating CO₂ hydrogenation selectivity toward C1 products, discussing remaining challenges, and highlighting future opportunities of CO₂ hydrogenation.

CO ₂加氢生产增值化学品为缓解能源危机和气候变暖提供了一条有前景的途径。高选择性CO ₂加氢对于降低分离和循环成本、提高生产效率具有重要意义。然而，由于复杂的反应网络和催化剂上多个活性位点的共存，这仍然是一个巨大的挑战。本综述重点关注CO ₂加氢生成一碳(C1) 产品的选择性控制，包括甲醇、CO 和CH ₄，它们是最简单的CO ₂加氢产品和基本化学构件。基于不同催化剂体系的发展，我们讨论了影响CO ₂加氢选择性的多因素，包括反应条件，如温度和压力，以及催化剂性能，如活性金属、金属分散体、载体和促进剂。我们总结了控制 CO ₂加氢对 C1 产品选择性的一般规则，讨论了剩余的挑战，并强调了 CO ₂加氢的未来机遇。