The interaction of CO with an attapulgite-supported Cu(II)Cl₂ catalyst has been examined in a micro-reactor arrangement. CO exposure to the dried, as-received catalyst at elevated temperatures leads to the formation of CO₂ as the only identifiable product. However, phosgene production can be induced by using a catalyst pre-treatment where the supported Cu(II)Cl₂ sample is exposed to a diluted stream of chlorine. Subsequent CO exposure at ∼370 °C then leads to phosgene production. In order to investigate the origins of this atypical set of reaction characteristics, a series of X-ray absorption experiments were performed that were supplemented by DFT calculations. XANES measurements establish that at the elevated temperatures connected with phosgene formation, the catalyst is comprised of Cu⁺ and a small amount of Cu²⁺. Moreover, the data show that unique to the chlorine pre-treated sample, CO exposure at elevated temperature results in a short-lived oxidation of the copper. On the basis of calculated CO adsorption energies, DFT calculations indicate that a mixed Cu⁺/Cu²⁺ catalyst is required to support CO chemisorption.

中文翻译：

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一氧化碳氯化成光气过程中氯化铜催化剂的结构行为

已经在微反应器布置中检查了CO与凹凸棒石负载的Cu（II）Cl ₂催化剂的相互作用。在高温下将CO暴露于干燥的，原样接收的催化剂中会导致形成CO ₂作为唯一可识别的产物。然而，光气的产生可以通过在负载的Cu（II）Cl _2上进行催化剂预处理来诱导。样品暴露于稀释的氯气中。随后在约370°C的CO暴露下会产生光气。为了研究这种非典型反应特征集的起源，进行了一系列X射线吸收实验，并通过DFT计算进行了补充。XANES测量确定，在与光气形成相关的高温下，催化剂由Cu ⁺和少量Cu ^2+组成。而且，数据表明，对于氯气预处理的样品而言，独特的是，在高温下暴露于CO会导致铜的短暂氧化。根据计算出的CO吸附能，DFT计算表明混合的Cu ⁺ / Cu ²⁺ 需要催化剂来支持CO化学吸附。