Kang Keke, Kakihara Sota, Higo Takuma, Sampei Hiroshi, Saegusa Koki, Sekine Yasushi
Department of Applied Chemistry, Waseda University, 3-4-1, Okubo, Shinjuku, Tokyo, 169-8555, Japan.
Chem Commun (Camb). 2023 Sep 14;59(74):11061-11064. doi: 10.1039/d3cc02399k.
Reverse water gas shift (RWGS) can convert CO into CO by using renewable hydrogen. However, this important reaction is endothermic and equilibrium constrained, and thus traditionally performed at 900 K or higher temperatures using solid catalysts. In this work, we found that RWGS can be carried out at low temperatures without equilibrium constraints using a redox method called chemical looping (CL), which uses the reduction and oxidation of solid oxide surfaces. When using our developed MGaO (M = Ni, Cu, Co) materials, the reaction can proceed with almost 100% CO conversion even at temperatures as low as 673 K. This allows RWGS to proceed without equilibrium constraints at low temperatures and greatly decreases the cost for the separation of unreacted CO and produced CO. Our novel gallium-based material is the first material that can achieve high conversion rates at low temperatures in reverse water gas shift using chemical looping (RWGS-CL). Ni outperformed Cu and Co as a dopant, and the redox mechanism of NiGaO is a phase change due to the redox of Ga during the RWGS-CL process. This major finding is a big step forward for the effective utilization of CO in the future.
逆水煤气变换(RWGS)可以利用可再生氢气将一氧化碳(CO)转化为二氧化碳(CO₂)。然而,这一重要反应是吸热反应且受限于平衡,因此传统上是在900K或更高温度下使用固体催化剂进行。在这项工作中,我们发现可以使用一种称为化学链(CL)的氧化还原方法在低温下进行逆水煤气变换且不受平衡限制,该方法利用固体氧化物表面的还原和氧化过程。当使用我们开发的MGaO(M = Ni、Cu、Co)材料时,即使在低至673K的温度下,反应也能以几乎100%的CO转化率进行。这使得逆水煤气变换能够在低温下不受平衡限制地进行,并大大降低了未反应的CO和生成的CO₂的分离成本。我们新型的镓基材料是第一种能够在化学链逆水煤气变换(RWGS-CL)中在低温下实现高转化率的材料。作为掺杂剂,Ni的表现优于Cu和Co,并且在RWGS-CL过程中,NiGaO的氧化还原机制是由于Ga的氧化还原导致的相变。这一重大发现为未来有效利用CO向前迈出了一大步。