分子筛骨架铁锚定孤立铂位点实现高效丙烷脱氢反应

doi:10.1016/S1872-2067(26)65003-6

摘要/Abstract

摘要： 丙烯是重要的化工原料, 应用广泛且需求不断扩大. 丙烷脱氢(PDH)制丙烯反应作为丙烯定向生产技术, 因原油依赖度低、生产效率高、环境影响小等优势, 备受研究者关注. 铂基催化剂因优异的C‒H键断裂能力, 被广泛应用于工业PDH生产工艺. 然而, 苛刻反应条件下严重的积碳沉积和不可逆的金属颗粒烧结引起的快速失活, 严重制约了该催化剂的发展. 解决该问题的策略之一是引入Sn, Zn等第二种金属, 以稳定Pt活性位点并调控其电子结构, 从而抑制裂化、深度脱氢等副反应, 有效提高催化剂的稳定性. 其中, 沸石分子筛封装的Pt基双金属催化剂, 凭借优异的骨架稳定作用、良好的孔道限域效应和微环境调控能力, 成为PDH研究的热点之一.
近年来, Pt-Fe双金属催化剂以其良好的催化性能和成本优势, 成为PDH的潜力催化剂, 但活性中心结构的有效构筑及准确解析依然面临挑战. 本文提出了一种简便的一锅法合成策略, 成功在纯硅MFI沸石纳米片(NS)内构建了原子级分散的Pt-O-Fe双金属活性中心. 该策略通过老化和氟离子调控晶体成核与生长, 在合成沸石纳米片的同时, 利用近中性合成条件和氟离子对金属物种的稳定作用, 将适量Fe引入沸石骨架, 并通过骨架Fe的锚定作用, 使Pt物种以高度分散态稳定存在, 最终形成热力学稳定的≡Si-O-Fe-O-Pt结构单元. 通过X-射线吸收光谱、集成微分相位对比-扫描透射电镜等多种表征手段, 系统证明了MFI沸石中骨架Fe可作为有效金属锚定位点, 通过形成强相互作用的≡Si-O-Fe-O-Pt基团, 显著增强孤立Pt物种在高温反应环境下的结构稳定性, 从而有效抑制其在苛刻反应条件下的迁移与团聚. 所制备的具有低Pt负载量及适宜Pt/Fe比例的0.3Pt2Fe@NS催化剂, 在550 °C PDH反应中展现出优越的催化性能: 丙烯生成速率达到48.0 mmol C₃H₆·g_cat^-1·h^-1, 选择性始终高于95%, 并在30 h持续反应中保持活性无衰减. 在更高反应空速的苛刻条件下, 丙烯生成速率可进一步提升至234.5 mmol C₃H₆·g_cat^-1·h^-1, 同时维持高于97%的丙烯选择性. 尤为重要的是, 该催化剂在多次氧化-再生循环中表现出完全可恢复的催化活性, 显示出优异的循环再生能力与工业应用潜力. 机理研究表明, 优化的Pt/Fe化学计量比可最大化双金属协同催化效应, 且该体系遵循双功能催化反应机制: 原子级分散的Pt位点主要负责丙烷分子中C‒H键的异裂活化, 而与之配位的骨架Fe位点则通过促进H*物种的溢流与重组, 协助完成氢气的脱附与催化循环闭环. 这一协同路径不仅显著提高了丙烷脱氢本征活性, 也有效抑制了副反应的发生与积碳的生成.
综上, 本文通过一锅法构筑原子级分散的Pt-O-Fe双金属活性中心, 开发出兼具高活性、高选择性及优异稳定性的丙烷脱氢催化剂, 并准确解析了其协同催化机制, 为理性设计抗烧结、易再生的高性能和高稳定性PDH工业催化剂提供了新的结构模型与设计思路.

关键词: 丙烷脱氢, 孤立铂, 分子筛骨架铁, MFI纳米片, 双金属位点

Abstract: The development of effective alkane dehydrogenation catalysts is essential to produce olefins from abundant shale gas. Commercial Pt-based propane dehydrogenation catalysts suffer from deactivation due to sintering and coke deposition, highlighting the need for substantial improvements in thermal stability and production efficiency. Herein, we present a facile one-pot strategy to create atomically dispersed bimetallic Pt-O-Fe motifs encapsulated within MFI zeolite nanosheet, serving as highly active and stable sites for propane dehydrogenation. Comprehensive characterization results reveal that the skeletal Fe (III) species in MFI zeolite act as anchoring sites, thereby stabilizing atomically dispersed Pt species through the unique linkages of ≡Si-O-Fe-O-Pt. The optimized 0.3Pt2Fe@NS catalyst, featuring high skeletal Fe content, low Pt loading, and ideal synergetic effect of Pt-Fe endowed by the suitable Pt-to-Fe ratio, achieves a propylene productivity of 48.0 mmol C₃H₆·g_cat^-1·h^-1 with >95% selectivity at 550 °C for 30 h without performance degradation. The 0.3Pt2Fe@NS catalyst also exhibits complete regenerability under harsh cycling conditions, establishing a new structure-performance paradigm for the design of industrial PDH catalysts.

Key words: Propane dehydrogenation, Isolated platinum, Skeletal iron, MFI zeolite nanosheets, Bimetallic sites

吕昕彤, 魏正昌, 邓欣, 柴玉超, 武光军, 李兰冬. 分子筛骨架铁锚定孤立铂位点实现高效丙烷脱氢反应[J]. 催化学报, DOI: 10.1016/S1872-2067(26)65003-6.

Xintong Lv, Zhengchang Wei, Xin Deng, Yuchao Chai, Guangjun Wu, Landong Li. Isolated Pt sites anchored by skeletal Fe in MFI zeolite nanosheets towards productive propane dehydrogenation[J]. Chinese Journal of Catalysis, DOI: 10.1016/S1872-2067(26)65003-6.

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