With the upgrading and obsoleting of electric refrigeration equipment, significant amounts of waste hydrochlorofluorocarbon (HCFCs) refrigerants are being generated, bringing serious ozone-depleting and global warming effects. HCFCs, containing chlorine and fluorine, have the potential to be converted into acids by mineralization. Hydrothermal technology possesses a tightly sealed environment and high thermal efficiency, providing significant advantages in treating volatile HCFCs. However, the stable C-F bonds and the by-product CClF=CH2 greatly impede the mineralization of HCFCs. Herein, an indium compound from waste CIGS (CuInxGa1−xSe2) was introduced to promote the process, and this strategy successfully increased the mineralization rates of organic chlorine and fluorine to 99.2 % and 95.7 %, respectively. The acid produced from HCFCs degradation was utilized for the selective leaching of metals in CIGS. Meanwhile, the leaching product InOOH catalyzed further degradation of HCFCs. We revealed that InOOH can adsorb reactants and provide interfaces, resulting in (i) the elongation of C-X (F, Cl) bonds; (ii) a reduction in the energy barrier of the CClF=CH2 degradation reaction. This study provides a promising approach and theoretical basis for the harmless treatment and resourceful utilization of waste refrigerants containing Cl and F.

中文翻译：

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一种新型酸性资源：废氢氯氟烃制冷剂在热液气氛下选择性浸出 Cu-In-Ga-Se （CIGS） 和催化矿化


随着电制冷设备的升级和淘汰，产生大量废弃的氢氯氟烃 （HCFC） 制冷剂，带来严重的臭氧消耗和全球变暖效应。含氯和氟的 HCFC 有可能通过矿化转化为酸。水热技术具有紧密密封的环境和高热效率，在处理挥发性 HCFC 方面具有显著优势。然而，稳定的 C-F 键和副产物 CClF=CH2 极大地阻碍了 HCFCs 的矿化。在此，引入了来自废 CIGS 的铟化合物 （CuInxGa1−xSe2） 来促进该过程，该策略成功地将有机氯和氟的矿化速率分别提高到 99.2 % 和 95.7 %。HCFC 降解产生的酸用于 CIGS 中金属的选择性浸出。同时，浸出产物 InOOH 催化了 HCFCs 的进一步降解。我们揭示了 InOOH 可以吸附反应物并提供界面，导致 （i） C-X （F， Cl） 键的伸长;（ii） CClF=CH2降解反应的能垒降低。本研究为含 Cl 和 F 的废弃制冷剂的无害化处理和资源化利用提供了一种有前途的方法和理论依据。