高分散的Pt促进氨分解中活性FexN的形成

doi:10.1016/S1872-2067(23)64465-1

摘要/Abstract

摘要：

在氢经济的背景下, 氨分解在制氢中起着重要作用. 铁基催化剂因价格低廉且活性适中而备受欢迎, 对大规模应用具有吸引力. 然而, 铁基催化剂向更高活性Fe_xN物种的转化较慢, 导致诱导期延长. 为了解决该问题, 本文研究了在氨分解中添加Pt对Fe_xN形成的影响. 结果表明, 即使添加少量(0.1 wt%)Pt, 也能显著提高Fe_xN的形成速率, 使其增加3倍以上. Pt通过反溢流促进H₂脱附, 相反, 反溢流暴露出更多发生氮化的Fe表面位点, 导致Fe_xN的形成. 高角度环形暗场扫描透射电子显微镜、X射线衍射和原位X射线吸收光谱表征揭示了Fe₂N活性物质的形成. H₂程序升温脱附、H₂程序升温还原和原位X射线吸收谱证实了氢反溢流和溢流效应的存在. 总之, 本文加深了对铁催化剂在氨分解中活性物种形成机制的理解, 为提高其催化性能提供了一个简单策略.

关键词: 氨分解, 氮化铁, 氮化, Pt促进, 氢反溢流

Abstract:

Ammonia decomposition plays an important role in hydrogen production, especially in the context of a hydrogen economy. Fe-based catalysts are a popular choice due to their affordability and moderate activity, making them attractive for large-scale applications. However, the transformation of Fe-based catalysts into more active Fe_xN species can be slow, resulting in a prolonged induction period. To address this issue, we investigated the effects of Pt addition on Fe_xN formation in ammonia decomposition. Our results show that even a slight Pt addition significantly enhances the Fe_xN formation rate, increasing it over threefold. Pt aids in H₂ desorption via reverse spillover, which, in turn, exposes more Fe surface sites where nitridation occurs, leading to the formation of iron nitride. Characterization via High-angle annular dark-field imaging scanning transmission electron microscopy, X-ray diffraction, and in situ X-ray absorption spectroscopy (XAS) revealed the formation of Fe₂N as active species, whereas temperature-programmed hydrogen desorption, temperature-programmed reduction by hydrogen, and in situ XAS supported the existence of H reverse spillover and spillover effects. Overall, our study provides an improved understanding of the active species formation mechanism of Fe catalysts in ammonia decomposition and offers a simple strategy for improving their catalytic performance.

Key words: Ammonia decomposition, Iron nitride, Nitridation, Pt promotion, H reverse spillover

Keshia Saradima Indriadi, 韩沛杰, 丁世鹏, 姚冰清, Shinya Furukawa, 何迁, 颜宁. 高分散的Pt促进氨分解中活性Fe_xN的形成[J]. 催化学报, 2023, 50: 297-305.

Keshia Saradima Indriadi, Peijie Han, Shipeng Ding, Bingqing Yao, Shinya Furukawa, Qian He, Ning Yan. Highly dispersed Pt boosts active Fe_xN formation in ammonia decomposition[J]. Chinese Journal of Catalysis, 2023, 50: 297-305.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64465-1

https://www.cjcatal.com/CN/Y2023/V50/I7/297

图/表 7

Fig. 1. Catalytic performance of Fe-based catalysts. (a) Conversion at 500 °C over 4 h shows different induction periods for the catalyst with and without Pt addition. (b) Plot for the quantification of the nitride formation rate, where k' is the slope of the fitted linear lines and represents the nitride formation rate. Reaction conditions: 500 °C, 12000 mL gcat-1 h-1.

Fig. 2. (a?c) STEM-HAADF imaging and the corresponding elemental mappings of as-prepared 0.1Pt-10Fe/SiO2 (passivated) using EDS. (d?f) Representative STEM-HAADF images of spent 0.1Pt-10Fe/SiO2 catalyst after 20 h of reaction, indicating the stability of Pt species on Fe particles. (g) A representative STEM-HAADF image and the corresponding EELS elemental maps of a catalyst particle from the spent catalyst, show the formation of iron nitride for spent catalysts.

Fig. 3. Formation and identification of iron nitride species. (a) XRD of catalysts before reaction and spent catalysts after 20 h of NH3 decomposition reaction at 500 °C. Reference cards of Fe (PDF #06-0696), Fe2O3 (PDF #39-1346), Fe3N (PDF #49-1662), Fe2N (PDF #72-2126 and FeN (PDF #88-2153) are also presented. (b) Fourier transform of k3-weighted χ EXAFS in situ spectra at different stages of the nitridation process performed at 500 °C with 40 mL min-1 5%NH3 (i) and close-up views of the time-series Fourier transform k3-weighted χ EXAFS in situ spectra overlaid (ii).

Table 1 Composition of catalysts.

Catalyst	Fe content^a (wt%)	N content ^b (wt%)	Fe/N ratio
10Fe/SiO₂	11.0	1.3	2.1
0.1Pt-10Fe/SiO₂	9.6	1.4	1.8

Fig. 4. Role of Pt in facilitating H reverse spillover shown through H2-TPD (a), whose peaks have been deconvoluted using a Bi-Gaussian fitting. H spillover is proven by investigating reduction behaviour through H2-TPR (b) and XANES (c)(i) during in situ reduction that can be quantitively compared using LCF of the experimental spectra (ii) with the reference spectra of Fe2O3, FeO, and Fe foil.

Fig. 5. The role of H2 reverse spillover in facilitating nitride formation rate. (a) Effect of H2 co-feeding on the nitride formation rate of the catalysts. Reactions were performed at 500 °C with a GHSV of 12000 mL g-1cat h-1 and P(NH3) = P(H2) = 0.5. (b) XRD of spent catalysts after 4 h of reaction with H2 co-feeding.

Fig. 6. Proposed mechanism for the role of Pt (single atoms or clusters) in facilitating reverse H spillover and enhancing the rate of nitride formation in iron catalysts.

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