磷化钴–磷酸钴修饰氮化钽基纳米花可见光催化CO₂还原性能  

Cobalt Phosphide-Cobalt Phosphate Modified Tantalum Nitride-Based Nanoflower for Visible Light Catalytic CO2 Reduction Performance

作　　者：崔玉 孟祥磊 

机构地区：[1]哈尔滨师范大学化学化工学院,黑龙江 哈尔滨

出　　处：《材料科学》2024年第4期369-378,共10页Material Sciences

摘　　要：过渡金属氮氧化物半导体光催化CO2还原技术具有商业化应用开发潜力。以Ta2O5@Ta3N5纳米花为前驱体,通过磷化技术成功制备CoP-Co3(PO4)2双修饰Ta2O5@Ta3N5纳米复合光催化材料。与底物Ta2O5@Ta3N5相比,Co3(PO4)2单修饰样品光催化还原CO2产物从CO转变为CH4,CH4选择性达100%,实现CO2深度还原。在模拟太阳光下,CoP-Co3(PO4)2共修饰样品还原CO2产物CO和CH4产率均提升,其电子利用效率分别是Ta2O5@Ta3N5和Co3(PO4)2单修饰样品的5.5倍和1.5倍。表面局域构建Co3(PO4)2/Ta3N5和CoP/Ta3N5n-n突变异质结构,调控表面电子结构,产生内建电场驱动光生电子向Co3(PO4)2和CoP的CB传输,提高光生电子输运效率。Co3(PO4)2修饰增加光催化CO2还原为CH4的活性中心,而CoP修饰增加光催化CO2还原为CO活性中心;此外,Co3(PO4)2修饰增加样品表面羟基含量,提升样品对CO2吸附能力,有利于生成CH4;而CoP的P缺陷及部分吸附水降低反应活化能,提高生成CO的催化速率和选择性。CoP-Co3(PO4)2双修饰为开发高性能钽基光催化CO2还原新材料提供新路径。Transition metal nitride semiconductor photocatalytic CO2 reduction technology has the potential for commercial application development. Using Ta2O5@Ta3N5 nanoflowers as precursors, CoP- Co3(PO4)2 modified Ta2O5@Ta3N5 nanocomposite photocatalytic material was successfully prepared through phosphorization technology. Compared to the substrate Ta2O5@Ta3N5, the CO2 reduction products of the Co3(PO4)2 single-modified sample changed from CO to CH4, with a selectivity of 100%, achieving deep reduction of CO2. Under simulated sunlight, the CO and CH4 yields of the CoP-Co3(PO4)2 co-modified sample for CO2 reduction were enhanced, with electronic utilization efficiencies 5.5 times and 1.5 times higher than those of the substrate Ta2O5@Ta3N5 and the Co3(PO4)2 single-modified sample, respectively. The surface-localized Co3(PO4)2/Ta3N5 and CoP/ Ta3N5n-n heterojunctions were constructed to regulate the surface electronic structure and generate a built-in electric field to drive the transfer of photogenerated electrons to the CB of Co3(PO4)2 and CoP, thereby improving the efficiency of photogenerated electron transport. Co3(PO4)2 modification increased the active centers for photocatalytic CO2 reduction to CH4, while CoP modification increased the active centers for photocatalytic CO2 reduction to CO. Additionally, Co3(PO4)2 modification increased the surface hydroxyl content of the sample, enhancing its CO2 adsorption capacity, which is beneficial for CH4 generation. Meanwhile, the P defects and partially adsorbed water of CoP reduced the reaction activation energy, thereby improving the catalytic rate and selectivity for CO production. The dual modification of CoP-Co3(PO4)2 provides a new pathway for developing high-performance tantalum-based photocatalytic CO2 reduction materials.

关 键 词：氮化钽 磷酸钴 磷化钴 CO₂还原 可见光催化 

分 类 号：O64[理学—物理化学]