Prussian blue analogs (PBAs) are promising catalysts in heterogeneous oxidation processes. The catalytic activity of PBAs relies on exposed crystal facets and accessible active sites on the PBA framework. Employing a heteroatom doping strategy using a rare earth element (La), we regulated the crystal structure and optimized the catalytic activity of CoFe PBA for peroxymonosulfate (PMS)-driven degradation of the antibiotic norfloxacin (NOR). The La atoms were mainly doped in the interstitial sites of the CoFe PBA cubic lattices, without affecting the electron distributions of Co and Fe metals or the face-centered cubic crystal phase of the coordination skeleton. La doping dominated the (111) and (100) as the main exposed facets of CoFeLa PBA, increasing the affinity of CoFeLa PBAs for PMS adsorption due to the higher surface energy of the two facets. Consequently, the activation energy considerably declined from 77.57 kJ/mol in CoFe PBA to 51.66 kJ/mol in CoFeLa PBA and the catalytic activity for PMS-driven NOR degradation was largely improved, which can reach 76.4 % removal of NOR within 15 min, with an increased initial rate constant of 0.095 min. O was proven as the main reactive specie responsible for NOR degradation in the PMS/CoFeLa system, and O· and SO· were verified as the important intermediates to generate O. Thus, La doping can effectively enhance the catalytic performance of PBA-based catalysts for organic pollutant removal.

中文翻译：

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CoFe 普鲁士蓝类似物的 La 掺杂可提高诺氟沙星降解的催化活性

普鲁士蓝类似物（PBA）是多相氧化过程中很有前途的催化剂。 PBA 的催化活性依赖于 PBA 框架上暴露的晶面和可接近的活性位点。采用稀土元素 (La) 的杂原子掺杂策略，我们调节了 CoFe PBA 的晶体结构并优化了过一硫酸盐 (PMS) 驱动的抗生素诺氟沙星 (NOR) 降解的催化活性。 La原子主要掺杂在CoFe PBA立方晶格的间隙位置，不影响Co和Fe金属的电子分布或配位骨架的面心立方晶相。 La掺杂主导了(111)和(100)作为CoFeLa PBA的主要暴露面，由于这两个面具有较高的表面能，增加了CoFeLa PBA对PMS吸附的亲和力。因此，活化能从 CoFe PBA 中的 77.57 kJ/mol 大幅下降到 CoFeLa PBA 中的 51.66 kJ/mol，PMS 驱动的 NOR 降解的催化活性大大提高，可在 15 分钟内达到 76.4% 的 NOR 去除率，初始速率常数增加 0.095 分钟。 O被证明是PMS/CoFeLa体系中NOR降解的主要活性物质，O·和SO·被证实是生成O的重要中间体。因此，La掺杂可以有效增强PBA基催化剂的催化性能用于去除有机污染物。