Research progress on the in-situ characterizations of iron-based FTS catalysts pretreatment process
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摘要:
铁基费托合成(FTS)催化剂通常以氧化物前驱体α-Fe2O3的形式存在,在不同预处理条件下转变为铁碳化合物FexCy后具有不同的催化活性,因此,研究催化剂预处理过程对费托合成反应具有重要意义。然而该过程中物相体系高度动态复杂,通过常规表征手段无法捕捉到铁基催化剂准确的变化信息。为了深入探究前驱体α-Fe2O3体系在不同预处理过程中的真实变化,需要借助多种原位表征技术获取催化剂物相、形貌及其表面结构和性质的动态变化数据,从而可实现催化剂预处理过程和后续FTS催化性能的有效关联。本工作系统综述了X射线衍射、透射电子显微镜、X射线光电子能谱、红外光谱和拉曼光谱等原位表征技术在铁基FTS催化剂预处理过程中的实验方法以及数据处理方法,以明晰催化剂前驱体复杂的结构性质变化过程,进而促进更高效铁基FTS催化剂的设计和开发。
Abstract:Fe-based Fischer-Tropsch synthesis (FTS) catalysts usually exist as the oxide precursor α-Fe2O3, which have different catalytic activities after being transformed to FexCy under different pretreatment conditions, so it is critical to study the pretreatment process of α-Fe2O3 for whole FTS reaction. However, the phases of Fe-based catalysts in such a process are highly dynamic and complex, and conventional characterizations cannot capture the accurate real-time information in the pretreatment reaction. Therefore, it is necessary and desired to apply various in-situ characterizations in this process, because they can obtain the dynamic changes of phase, morphology, surface structure and properties of the catalyst. And then a relationship between the pretreatment process and the subsequent catalytic performance of FTS will be effectively and reasonably established. This review presents a systematic summary of the experimental and data processing methods in in-situ characterizations of X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, infrared spectroscopy and Raman spectroscopy during the pretreatment of Fe-based FTS catalysts. These characterizations can clarify the complex structure and surface property changes of catalyst precursors and thus will facilitate the design and development of more efficient Fe-based FTS catalysts.
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图 1 (a)先H2后合成气,(b)CO,(c)合成气气氛下Rietveld精修的铁基催化剂物相相对丰度;在(d)2% CO/He和(e)2% CO/ 8% H2/He气氛下,Rietveld精修的Fe3O4平均晶粒尺寸[33, 35]
Figure 1 Rietveld refinement of relative abundance of iron oxide in (a) syngas after H2, (b) CO and (c) syngas; Rietveld refinement of average crystal size of Fe3O4 in (d) 2% CO/He and (e) 2% CO/ 8% H2/He [33, 35](with permission from Elsevier and Wiley)
图 2 α-Fe2O3催化剂的in-situ XRD谱图:(a)高μC条件下预处理及其(b)随后的FTS过程;(d)低μC条件下预处理和及其(e)随后的FTS过程中;(c)高μC催化剂和(f)低μC催化剂在FTS条件下k1傅里叶变换Fe K边原位EXAFS数据[39]
Figure 2 In-situ XRD patterns of the α-Fe2O3 catalyst evolution during (a) pretreatment in high µC and (b) subsequent FTS condition; (d) pretreatment in low µC and (e) subsequent FTS condition; phase corrected, k1 weighted Fourier-transformed Fe K-edge EXAFS data of the α-Fe2O3 catalyst samples during FTS, (c) high µC catalyst and (f) low µC catalyst [39] (with permission from ACS Publications)
图 3 (a)常温,(b)400 ℃,(c)700 ℃时Fe/BN的TEM照片和FePt尺寸分布(插图);(d)保持900 ℃15 min后的HRTEM照片;((e)–(g))FePt被h-BN纳米片包裹的HRTEM图像[44]。
Figure 3 TEM images and FePt size distribution (inset) of Fe/BN at (a) RT, (b) 400 ℃, (c) 700 ℃; (d) HRTEM image of FP/BN at 900 ℃ after exposure for 15 min; ((e)–(g)) HRTEM images of FePt nanoparticles enveloped by h-BN nanosheets [44](with permission from Elsevier)
图 4 (a)α-Fe2O3转变为γ-Fe2O3的in-situ HRTEM照片,((b),(c))分别是(a)中红色方框区域b和c的衍射图,((d),(e))b和c区域的EELS光谱,(f)ZnFe2O4@Co3O4在纯H2还原过程中获得的STEM-HAADF图像,插图为EELS光谱图像获得的复合元素图(Co:绿色;Zn-Fe:橙色)[30, 46]
Figure 4 (a) In-situ HRTEM of the transformation from α-Fe2O3 to γ-Fe2O3, ((b), (c)) The diffractograms from red boxed regions b and c, in (a), respectively, ((d), (e)) EELS spectra from the regions of red boxes b and c in (a), (f) STEM-HAADF images of ZnFe2O4@Co3O4 obtained during the in-situ TEM reduction in pure H2, with inset showing the composite elemental map obtained from the EELS spectrum image (Co: green; Zn-Fe :orange)[30, 46] (with permission from Elsevier and ACS Publications)
图 5 (a)纳米α-Fe2O3和(b)块状α-Fe2O3在氢气中处理过程中的Fe 2p3/2 XPS谱图,箭头表示纳米颗粒样品中的等吸光点;不同气氛下FeCeNa催化剂的((c), (d))O 1s和((e), (f))Ce 3d in-situ XPS光谱谱图[32, 53]
Figure 5 (a) Fe 2p3/2 XPS spectra during treatment of (a) the nanoparticles and (b) bulk iron oxide in H2, the arrow indicates the isosbestic point in the nanoparticulate sample; in-situ XPS spectra of ((c), (d)) O 1s and ((e), (f)) Ce 3d of FeCeNa catalysts in different atmospheres[32, 53](with permission from Elsevier and Wiley)
图 6 (a)(s1)Al2O3/α-Fe2O3 = 1,(s2)SiO2/α-Fe2O3 = 1,(s3)α-Fe2O3活化后催化剂的in-situ CO-DRIFTS光谱谱图;(b)SiO2负载的铁基催化剂的in-situ DRIFTS光谱谱图[18, 64]
Figure 6 (a) in-situ CO-DRIFTS spectra of (s1) Al2O3/α-Fe2O3 = 1, (s2) SiO2/α-Fe2O3 = 1, (s3) α-Fe2O3; (B) in-situ DRIFTS spectra of SiO2-supported iron based catalyst[18, 64] (with permission from Elsevier and Springer)
图 8 (a)35FeK/m-ZrO2和(b)35FeK/t-ZrO2催化剂的in-situ Raman谱图,实验条件:1 atm、30 mL/min、10% CO/Ar和10 ℃/min的加热速率;(c)350 ℃下CO预处理300 min后35Fe K/m-ZrO2和35FeK/t-ZrO2催化剂的拉曼光谱谱图[72]
Figure 8 In-situ Raman spectra of (a) 35FeK/m-ZrO2 and (b) 35FeK/t-ZrO2, measurement conditions: 1 atm, 30 mL/min, 10% CO/Ar, and the heating rate of 10 ℃/min, (c) Raman spectra of 35FeK/m-ZrO2 and 35FeK/t-ZrO2 catalysts after the CO prereduction at 350 ℃ for 300 min[72] (with permission from ACS Publications)
表 1 铁基催化剂的in-situ XPS、FT-IR和Raman表征技术的常用参数
Table 1 Common parameters of in-situ XPS, FT-IR and Raman characterization techniques for iron-based catalysts
Phase XPS[18, 19]/
eVOrigin FT-IR[20-22]/
cm−1Origin Raman[23, 24]/
cm−1α-Fe2O3 711.0
529.8Fe 2p3/2
O 1s650, 575,
525, 485,
440, 400,
385, 360,
300Fe–O 613, 500,
412, 299,
247, 225,
1320Fe3O4 709.0
530.2Fe 2p3/2
O 1s580
400Fe–O 676
550FeO 709.0
530.2Fe 2p3/2
O 1s490
425Fe–O 210, 390
480, 652α-Fe 706.8
720.3Fe 2p3/2
Fe 2p1/22040−
1980CO
surface adsorptionχ-Fe5C2 707.0
719.9Fe 2p3/2
Fe 2p1/22015 D band:
1380
G band:
1580θ-Fe3C 707.9
720.6Fe 2p3/2
Fe 2p1/22030 -
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