Over the last two decades, polymers with superior H₂/CO₂ separation properties at 100–300 °C have gathered significant interest for H₂ purification and CO₂ capture. This timely review presents various strategies adopted to molecularly engineer polymers for this application. We first elucidate the Robeson's upper bound at elevated temperatures for H₂/CO₂ separation and the advantages of high‐temperature operation (such as improved solubility selectivity and absence of CO₂ plasticization), compared with conventional membrane gas separations at ~35 °C. Second, we describe commercially relevant membranes for the separation and highlight materials with free volumes tuned to discriminate H₂ and CO₂, including functional polymers (such as polybenzimidazole) and engineered polymers by cross‐linking, blending, thermal treatment, thermal rearrangement, and carbonization. Third, we succinctly discuss mixed matrix materials containing size‐sieving or H₂‐sorptive nanofillers with attractive H₂/CO₂ separation properties.

中文翻译：

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分子工程聚合物膜，用于在100–300°C下分离H2 / CO2

在过去的二十年中，在100–300°C下具有优异H ₂ / CO ₂分离性能的聚合物引起了人们对H ₂纯化和CO ₂捕集的极大兴趣。这份及时的评论介绍了针对该应用对聚合物进行分子工程设计的各种策略。我们首先阐明了在高温下进行H ₂ / CO ₂分离的Robeson上限以及高温操作的优点（例如，提高的溶解度选择性和不存在的CO ₂与在约35°C的常规膜气体分离相比。其次，我们描述了与商业相关的膜，用于分离，并突出显示了可自由调节体积的材料，以区分H ₂和CO ₂，包括功能性聚合物（例如聚苯并咪唑）和通过交联，共混，热处理，热重排和工程改造的聚合物碳化。第三，我们简要讨论了混合基质材料，其中包含具有吸引人的H ₂ / CO ₂分离特性的筛分或H ₂吸附纳米填料。