Co-Based Catalysts Supported on Silica and Carbon Materials: Effect

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Co-Based Catalysts Supported on Silica and Carbon Materials: Effect of Support Property on Cobalt Species and Fischer-Tropsch Synthesis Performance Xin Li, Mehar U Nisa, Yao Chen, and Zhenhua Li Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.8b05451 • Publication Date (Web): 30 Jan 2019 Downloaded from http://pubs.acs.org on February 7, 2019

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Industrial & Engineering Chemistry Research

Co-Based Catalysts Supported on Silica and Carbon Materials: Effect of Support Property on Cobalt Species and FischerTropsch Synthesis Performance Xin Li, Mehar U Nisa, Yao Chen, Zhenhua Li* Key Lab for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin University, Tianjin 300072, China

Corresponding author * Email address: [email protected]; Tel.: +86-022-27405484 1

ACS Paragon Plus Environment

Industrial & Engineering Chemistry Research 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ABSTRACT: The inﬂuence of different support surfaces and physical structures on cobalt species and catalytic Fischer-Tropsch synthesis (FTS) performance has been investigated by using silica or mesoporous carbon as support. All the three catalysts Co/SBA-15, Co/SiO2 and Co/CMK-3 behaved differently in FTS test and showed characteristic cobalt species. After calcination in argon, Co3O4 was prominent on both Co/SBA-15 and Co/SiO2 because of the stronger metal-support interaction. However, the weaker metal-support interaction on Co/CMK-3 coupled with the autoreduction of cobalt oxide facilitated the formation of more CoO on the support surface. On account of the higher reducibility and specific surface area, Co/SBA-15 exhibited higher CO conversion in FTS than another two as-synthesized catalysts. SBA-15 and CMK-3 possess well-ordered channel structure which favors mass transport and diffusion while diffusion inhibits hydrocarbon chain growth. The highest C5+ and C11-17 selectivity were observed over Co/SiO2 without regular channels enabling enough intermediates residence time for carbon chain growth.

KEYWORDS: cobalt species; support surface; physical structure; metal-support interaction; Fischer-Tropsch synthesis

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1. INTRODUCTION Concerning the crude oil depletion in the world, synthesizing clean fuels via FischerTropsch synthesis (FTS) has been a subject of concern since the Second World War.1-3 The FTS process uses syngas as raw material that comes out of natural gas, coal, biomass and so on to get hydrocarbon compounds directly. Cobalt, ferrum and ruthenium have been applied as active phase for their suitable hydrogenation capacity.1, 4, 5 Among them, Rubased catalysts have been applied restrictively because of their expensiveness. Comparatively, Fe-based or Co-based catalysts are widely researched owing to their high reactivity and acceptable price. Fe-based catalysts could convert CO-rich syngas into more oxygenated compounds due to their high water-gas-shift activity.5, 6 Co-based catalysts have stronger resistance to deactivation, possessing higher catalytic FTS activity at lower reaction temperature and stability than Fe catalysts, accompanied with lower selectivity of impurities and by-products such as oxygenated compounds, 7, 8 So, Co-based catalysts show more potential application. It was generally accepted that the support property had crucial effect on Co-based catalyst for FTS performance. The Co-based catalyst with not only good Co dispersion but also high reduction degree is desired for improving FTS performance. In fact, however, it is often difficult to do both, either high dispersion with low reduction degree or high reduction degree with low dispersion was obtained. Silica and alumina are most commonly used supports among the oxide supports, in which alumina has more Brönsted and Lewis 3



acid sites. More acid sites on alumina surface caused stronger metal-support interaction, which led to lower reducibility and aided the dispersion of corresponding catalysts.9 Meanwhile, the selectivity of light hydrocarbons and product distribution in FTS can be affected by acid cracking sites.10 Without Brönsted acid sites from alumina, silica as support has moderate metal-support interaction and little influence over product selectivity. Khodakov et al.11 studied the influence of porosity on the dispersion and reducibility of cobalt species in mesoporous silica and discovered that smaller Co3O4 particles were much harder to be reduced because of cobalt silicate ( Co/SiO2> Co/CMK-3, which was due to the different metal-support interaction also confirmed by the FT-IR spectra analysis. The higher energy of the lattice oxygen on Co/SBA-15 means higher metal-support interaction.34 14


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Table 1. XPS data of the as-prepared catalysts Binding energy (eV)

Co 2p1/2

Co 2p3/2

△(Co 2p1/2-Co 2p3/2)

O 1s

Co/SBA-15

796.6

781.3

15.3

533.2

Co/SiO2 Co/CMK-3

795.7 797.4

780.6 781.5

15.1 15.9

532.8 532.1

The TEM images Figure 3 (a-c) show crystal lattice of as-prepared catalysts, where particles with a d spacing of 0.244 nm were associated with the (311) Co3O4 facet [JCPDS 42-1467] on the Co/SBA-15 and Co/SiO2, and particles with a d spacing of 0.210 nm were related to the (200) CoO facet [JCPDS 43-1004] on Co/CMK-3 catalyst, verifying the results of characterization analysis before.

Figure 3. HRTEM images of fresh Co-based catalysts: (a) Co/SBA-15, (b) Co/SiO2, (c) Co/CMK-3.

The H2-TPR profiles of as-prepared catalysts are shown in Figure 4. Clearly, all three catalysts present two main reduction regions. They are attributed to the reduction of Co3O4 to CoO at 213.5-285 °C and CoO to Co0 at 330.9-432.8°C respectively. Whereas, catalysts 15



supported on silicon carriers have higher TPR peak temperature than that on carbon substrate. It is because that there are many silica hydroxyl groups on the silica supports surface, like geminal groups [(SiO)2–Si–(OH)2] and isolated groups [(SiO)3Si–OH],44 which caused stronger metal-support interaction and higher reduction temperature due to a higher hydrophilicity. On the contrary, CMK-3 with hydrophobic and inert surface efficiently rules out a possibility of strong metal-support interactions,30 which enables the autoreduction of Co3O4 and a lower reduction temperature.24, 25

Ⅰ:Co3O4-CoO

Ⅱ:CoO-Co cobalt metasilicate

Co/SBA-15

TCD Signal (a.u.)

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Ⅰ:Co3O4-CoO

Ⅱ:CoO-Co

Co/SiO2 Carbon gasification Ⅱ:CoO-Co Ⅰ:Co3O4-CoO

Co/CMK-3 100

200

300

400

500

600

700

Temperature (°C)

Figure 4. H2-TPR curves of the catalysts: Co/SBA-15, Co/SiO2, Co/CMK-3

The extent of different catalysts reducibility was then correlated to the area of the first two H2 consumed peaks (depends linearly on the H2 consumption). In order to compare the reducibility degree of the catalysts, the reducibility ratio of Co/SBA-15 was defined as 1.00 and then the relative reducibility ratios of another two catalysts was estimated.32 As it can 16


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be seen from Table S2, the reduction degree for Co/SBA-15 was the highest, owing to the bigger average crystal size of Co3O4 which means it easier to be reduced on Co/SBA-15, meanwhile, with smaller CoO particles, Co/CMK-3 had the lowest reduction degree.11 While, area ratios of the second reduction peak (CoO to Co0) to the first reduction peak (Co3O4 to CoO) were 3.3, 3.7 and 7.1, respectively, for Co/SBA-15, Co/SiO2 and Co/CMK3, confirming more CoO rather than Co3O4 on CMK-3. From Figure 4, it can been seen that Co/CMK-3 has a big gasification peak over 450 °C under 10% H2/Ar atmosphere, indicating that the structure of CMK-3 can’t remain stable in the reductive condition with high temperature. There is also a small TPR profile’s peak attributed to irreducible cobalt silicate on Co/SBA-15, confirming the stronger metal-support interaction, which was considered to be formed in H2 atmosphere at high temperature.14, 45 Table 2 lists the cobalt dispersion and particle size of CoOx and Co0. The particle size deduced from XRD and H2-TPD data has same varying tendency: the CoOx or Co0 particle size on both SBA-15 and SiO2 is larger than that on CMK-3. TEM analysis gives a little different result with similar Co0 particle size on SiO2 and CMK-3. Many factors could affect metal particle size. One major factor is the chemical bonding between metal and the support that was formed during decomposition of cobalt nitrate, nucleation and growth of metal oxide crystallites.21 For silica substrate supports (SBA-15 and SiO2), excess hydrophilic groups (silica hydroxyl groups) limited the movement and distribution of impregnating solution. On silica support, the Co species were selectively deposited on the 17



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outermost mouths of the mesopores due to the excess hydrophilic groups. The excess hydrophilic groups also led to a stronger interaction between metal ion and support, which decreased the diffusion rate of Co2+ ions inside mesopores during solution evaporation process and calcination process.10 Therefore, larger Co3O4 formed on SBA-15 and SiO2. And larger Co3O4 were easy to be reduced to metallic cobalt than smaller ones.11 However, an inert surface and absence of hydrophilic groups over the surface of CMK-3 facilitated diffusion of Co2+ inside mesopores, leading to better CoO distribution and smaller CoO nanoparticles after calcination. Consequently, the metal-support interaction on CMK-3 was weaker despite of the well distributed smaller cobalt oxides, which was more difficult to be reduced to Co0 than larger cobalt oxides.11 The reduction degree is indicated by the TPR profiles, in which the Co/CMK-3 has the smallest peak area (AII in Table 1) corresponding to the reduction of CoO.

Table 2. Particle size and dispersion of catalysts estimated from XRD, TEM and H2-TPD dCoOxa(XRD)b

dCo0(TEM)c

dCo0(H2-TPD)d

Dispersione

(nm)

(nm)

(nm)

(%)

Co/SBA-15

13.6

7.1

11.9

8.1

Co/SiO2

14.0

4.5

8.9

10.8

Co/CMK-3

3.9

4.9

5.8

16.6

Catalyst

a

For Co/SBA-15 and Co/SiO2, CoOx means Co3O4 and for Co/CMK-3, CoOx means CoO.

b Average

c The

crystal sizes of CoOx calculated from the Scherrer equation: d=

0.9λ B cos θB

×

180° π

catalysts were reduced first and then passivated in a gas mixture of 1 vol.% O2 in Ar. 18


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d

Average crystal sizes of Co0 : d=96/Dispersion.

e

Supposing a cobalt adsorbs an H atom (H2/Co= 2). The dispersion is uncorrected.

3.3 The cobalt loss and aggregation. EDS mapping was conducted on the as-prepared catalysts as well as the used catalysts to estimate the content and distribution state of cobalt on the outer surface of the supports. Figure S4 gives the SEM micrographs of selected area and the elemental distributions of Si, O and Co on fresh Co/SBA-15. Clearly, the substrate elementals like Si and O uniformly disperse on the catalysts, while the relatively low signals of cobalt confirm the low content on the outer surface of supports and means most of cobalt located inside the mesopores of SBA-15. Table 3 summarizes the surface cobalt contents on the fresh and used catalyst. Obviously, for all three catalysts the outer surface cobalt content increased after FTS reaction, Co/CMK-3 and Co/SiO2 have bigger cobalt content increase amplitude compared to Co/SBA-15. Possibly because the weaker metalsupport interaction of Co/CMK-3 and lack of regular channels to confine cobalt particles of SiO2, more cobalt particles ran out of channels to the outer surface. According to the result of TPR profiles, channels destroyed partly of CMK-3 under a certain reaction atmosphere at high temperature also incurs cobalt loss, which was considered to be an important cause of decreased catalyst activity.32

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Table 3. SEM mapping results of the catalysts Co content

Catalyst

a

Co/SBA-15

Co/SiO2

Co/CMK-3

As-prepared, atom.%

3.39

1.8

0.69

Used, atom.%

5.91

9.15

2.38

ΔCo content, %a

74

408

245

The increase of the Co content on the outer surface of the supports was calculated by the formula: ΔCo=

Co content of used catalyst−Co content of as-prepared catalyst Co content of as-prepared catalyst

×100%

Figure 5 shows TEM images of reduced Co/CMK-3 and used Co/CMK-3. The former was reduced in hydrogen for 10 h at 400 °C followed by a passivation treatment in a gas mixture of 1 vol.% O2 in Ar at ambient temperature. The cobalt crystallites had well dispersion on CMK-3 after reduction (Table 2). This fact could positively prove that the Co2+ diffused well inside the channels of CMK-3 due to the hydrophobic surface, which caused better dispersion of Co0. After FTS reaction, the particles on Co/CMK-3 had remarkable growth after reaction, because cobalt particles migrate more easily over the hydrophobic and inert support surface.46 The aggregation of cobalt particles caused continuous drop in the activity during the FTS reaction.

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Figure 5. TEM images of (a) reduced Co/CMK-3 and (b) used Co/CMK-3.

3.4. Catalyst activity and product selectivity. The FTS activity and selectivity results after initial 22 h catalyst stabilization have been summarized in Table 4. The curves of CO conversion are presented in Figure 6, exhibiting different stability patterns of each catalyst. In Figure 6, Co/SBA-15 and Co/SiO2 are more stable and Co/SBA-15 has the highest CO conversion reaching 74.6%. At the same time, Co/CMK-3 has poorest stability among all, and its CO conversion dropped from a conversion of 57% to 28%, about 50.9% decline due to aggregation of cobalt particles as well as the collapse of carbon support.32, 46 There are many factors can influence the stability of the catalysts; the more critical factor of the better stability for Co/SBA-15 can be attributed to its more hydrophilic surface with a stronger metal–support interaction inhibiting cobalt sintering. Just as we know, higher reducibility can produce more active sites for FTS reaction,32, 47 therefore Co /SBA-15 has the highest CO conversion. Co/SBA-15 and Co/CMK-3 both exhibit higher initial CO conversion than Co/SiO2. It can be ascribed to their highly ordered mesoporous structure 21



which are beneficial for the adsorption and diffusion process.48, 49

100

Co/SBA-15 Co/SiO2 Co/CMK-3

90

CO Conversion (%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

80 70 60 50 40 30 20 10 0 0

2

4

6

8

10

12

14

16

18

20

22

Time on stream (h)

Figure 6. CO conversion of different catalysts

Besides the influence of number of active sites, cobalt particle size was also reported to affect the catalytic activity. The smaller cobalt particles (less than 7 nm), the longer CHx residence times and the fewer surface active sites.50 Co/SBA-15 had Co0 particle size greater than 7nm, a certain size value greater than which the TOF gradually becomes constant, 21, 50, 51 so the cobalt on SBA-15 with particle size greater than 7 nm performed better activity than Co/SiO2 and Co/CMK-3. For Co/SBA-15, possessing bigger cobalt particles also attributes to its more hydrophilic surface with a strong metal–support interaction which is beneficial to form bigger Co3O4 bulks that are easily reduced to bigger Co0 particles. Figure S6 illustrates C5+ hydrocarbon distribution over the three catalysts. Co/CMK-3 and Co/SBA-15 have higher C5-C10 selectivity, however, Co/SiO2 has better performance 22


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on hydrocarbon chain growth and provides the highest amounts of C11-C24 of three catalysts. Previous research of Xiong et al.21 had found the cobalt particle size influenced C5+ selectivity with a positive correlation. The size of Co0 particles on Co/SiO2 and Co/CMK3 was nearly the same, so the difference in C5+ selectivity may be due to the order degree of their mesoporous structure. High ordered mesoporous structure is beneficial for diffusion of reactants and hydrocarbons which in turn may reduce the residence time to form long chain hydrocarbons. Iglesia1 also found that support structure affected on the rate of diffusion and residence time of intermediate products. The higher diffusion rate, the greater chain growth probability. Comparison between C5+ selectivity of Co/SiO2 and Co/SBA-15 also verified the previous result. Though particle size was bigger on Co/SBA15, the C5+ selectivity was lower because of the better diffusion. Thus, the physical structure of support has significant effect on FTS performance, which should be considered for rational design of catalysts. Table 4. The FTS activity and product selectivity results a CO2 CO Hydrocarbon Selectivity (%) Conversion Selectivity (%) (%) CH4 C2 C3 C4 C5+ C5-10 C11-17 C18+

Catalyst

α

TOF (S-1)b

20Co/SBA-15

74.6

1.6

21.4 2.3

4.4 3.7

68.3 55.0 37.3

7.7

0.79

0.061

20Co/SiO2

45.2

0.5

15.3 1.6

3.9 4.0

75.3 40.3 47.4 12.3

0.81

0.027

20Co/CMK-3

35.3

0.0

25.2 1.7

5.1 5.7

62.2 64.7 30.2

0.76

0.014

a Reaction b Turnover

5.1

conditions: 0.8 g cat., T = 230 °C, P = 2.0 MPa, n(H2)/n(CO) = 2; WHSV = 6750 mL/(h·g) frequency of CO

23



4. CONCLUSION By using three supports with different materials and physical structures, the catalysts of Co/SBA-15, Co/SiO2 and Co/CMK-3 showed differences in surface cobalt species and FTS performance. Having much surface functional groups of silanol (Si–OH), SBA-15 played a key role in facilitating the formation of larger cobalt particle size, which endowing Co/SBA-15 with highest reduction degree. Due to the higher reducibility and higher specific surface area, Co/SBA-15 showed better performance in FTS than either Co/SiO2 or Co/CMK-3. CO conversion rates reached 74.6% and TOF reached 0.061 S-1 on Co/SBA15. The metal-support interaction on CMK-3 was weaker due to its hydrophobic properties and carbon substrate enabled the autoreduction of cobalt oxides to form smaller CoO that was more difficult to be reduced to Co0 than larger ones.11, 24, 25 Thus the Co/CMK-3 had lower FTS initial activity than Co/SBA-15. Cobalt particles migrated more easily over the hydrophobic and inert support surface, which facilitated the aggregation of cobalt particles.46 The aggregation of cobalt particles resulted in continuous drop in the activity during the FTS reaction. The physical structure of supports also have significant effect on FTS performance. SBA-15 and CMK-3 have well-ordered channel structure which is good for mass transport and diffusion. Since diffusion inhibits hydrocarbon chain growth, C 5+ selectivity of Co/SBA-15 and Co/CMK-3 were about 7% and 13.1% less than that of Co/SiO2. For Co/SBA-15 catalyst, optimization study should be considered to improve metal dispersion degree on SBA-15, and the autoreduction behavior of CMK-3 supported 24


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catalysts might provide a new sight to design and synthesis of catalysts when solved the gasification of carbon skeleton.

ASSOCIATED CONTENT Supporting Information SXRD profiles of CMK-3 and SBA-15; Nitrogen adsorption-desorption isotherms of samples; FT-IR spectra of the as-prepared catalysts; the absorption bends of Si–O–Si and hydroxyl groups on silicon support; SEM images and elemental mapping of fresh Co/SBA15; the FTS results; and tables of textural properties of different samples obtained by N2 adsorption-desorption, of Co dispersion and particle size. This file is available free of charge.

AUTHOR INFORMATION Corresponding author * Email address: [email protected]; Tel.: +86-022-27405484 Notes The authors declare no competing financial interest.

ACKNOWLEDGEMENT We thank the financial support from the National Natural Science Foundation of China 25



(21506154) and the Program of Introducing Talents of Discipline to Universities (B06006).

REFERENCE (1) Iglesia, E. Design, Synthesis, and Use of Cobalt-based Fischer–Tropsch Synthesis Catalysts. Appl. Catal., A 1997, 161, 59-78. (2) Van Steen, E.; Claeys, M.; Möller, K. P.; Nabaho, D. Comparing a Cobalt-based Catalyst with Iron-based Catalysts for the Fischer-Tropsch XTL-process Operating at High Conversion. Appl. Catal., A 2018, 549, 51-59. (3) Zhang, Q.; Cheng, K.; Kang, J.; Deng, W.; Wang, Y. Fischer-Tropsch Catalysts for the Production of Hydrocarbon Fuels with High Selectivity. ChemSusChem. 2014, 7, 12511264. (4) Li, W. Z.; Liu, J. X.; Gu, J.; Zhou, W.; Yao, S. Y.; Si, R.; Guo, Y.; Su, H. Y.; Yan, C. H.; Li, W. X.; Zhang, Y. W.; Ma, D. Chemical Insights into the Design and Development of Face-Centered Cubic Ruthenium Catalysts for Fischer-Tropsch Synthesis. J. Am. Chem. Soc. 2017, 139, 2267-2276. (5) Pham, T. H.; Qi, Y.; Yang, J.; Duan, X.; Qian, G.; Zhou, X.; Chen, D.; Yuan, W. Insights into Hägg Iron-Carbide-Catalyzed Fischer–Tropsch Synthesis: Suppression of CH4 Formation and Enhancement of C–C Coupling on χ-Fe5C2 (510). ACS Catal. 2015, 5, 2203-2208. (6) Santos, V. P.; Wezendonk, T. A.; Jaen, J. J.; Dugulan, A. I.; Nasalevich, M. A.; Islam, 26


Page 26 of 35

Page 27 of 35 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


H. U.; Chojecki, A.; Sartipi, S.; Sun, X.; Hakeem, A. A.; Koeken, A. C.; Ruitenbeek, M.; Davidian, T.; Meima, G. R.; Sankar, G.; Kapteijn, F.; Makkee, M.; Gascon, J. Metal Organic Framework-mediated Synthesis of Highly Active and Stable Fischer-Tropsch Catalysts. Nat. Commun. 2015, 6, 6451. (7) Zhang, T.; Wu, J.; Xu, Y.; Wang, X.; Ni, J.; Li, Y.; Niemantsverdriet, J. W. Cobalt and Cobalt Carbide on Alumina/NiAl(110) as Model Catalysts. Catal. Sci. Technol. 2017, 7, 5893-5899. (8) Yang, J.; Ma, W.; Chen, D.; Holmen, A.; Davis, B. H. Fischer–Tropsch Synthesis: A Review of the Effect of CO Conversion on Methane Selectivity. Appl. Catal., A 2014, 470, 250-260. (9) Dragoi, B.; Dumitriu, E.; Guimon, C.; Auroux, A. Acidic and Adsorptive Properties of SBA-15 Modified by Aluminum Incorporation. Micropor. Mesopor. Mat. 2009, 121, 717. (10) Cho, J. M.; Ahn, C. I.; Pang, C.; Bae, J. W. Fischer–Tropsch Synthesis on Co/AlSBA-15: Effects of Hydrophilicity of Supports on Cobalt Dispersion and Product Distributions. Catal. Sci. Technol. 2015, 5, 3525-3535. (11) Khodakov, A. Y.; G.-C, A.; Bechara, R.; Villain, F. Pore-size Control of Cobalt Dispersion and Reducibility in Mesoporous Silicas. J. Phys. Chem. B 2001, 105, 9805– 9811. (12) Munnik, P.; de Jongh, P. E.; de Jong, K. P. Control and Impact of the Nanoscale 27



Distribution of Supported Cobalt Particles Used in Fischer-Tropsch Catalysis. J. Am. Chem. Soc. 2014, 136, 7333-40. (13) Ghampson, I. T.; Newman, C.; Kong, L.; Pier, E.; Hurley, K. D.; Pollock, R. A.; Walsh, B. R.; Goundie, B.; Wright, J.; Wheeler, M. C.; Meulenberg, R. W.; DeSisto, W. J.; Frederick, B. G.; Austin, R. N. Effects of Pore Diameter on Particle Size, Phase, and Turnover Frequency in Mesoporous Silica Supported Cobalt Fischer–Tropsch Catalysts. Appl. Catal., A 2010, 388, 57-67. (14) Khodakov, A. Y.; Zholobenko, V. L.; Bechara, R.; Durand, D. Impact of Aqueous Impregnation on the Long-range Ordering and Mesoporous Structure of Cobalt Containing MCM-41 and SBA-15 Materials. Micropor. Mesopor. Mat. 2005, 79, 29-39. (15) Martıń ez, A.; López, C.; Márquez, F.; Dı́az, I. Fischer–Tropsch Synthesis of Hydrocarbons over Mesoporous Co/SBA-15 Catalysts: The Influence of Metal Loading, Cobalt Precursor, and Promoters. J. Catal. 2003, 220, 486-499. (16) Zhao, Y.; Li, J.; Zhang, Y.; Chen, S.; Liew, K. Al-SBA-16 Supported Cobalt Catalysts for the Fischer-Tropsch Production of Gasoline-Fraction Hydrocarbons. ChemCatChem. 2012, 4, 1926-1929. (17) Chen, Q.; Liu, G.; Ding, S.; Chanmiya Sheikh, M.; Long, D.; Yoneyama, Y.; Tsubaki, N. Design of Ultra-active Iron-based Fischer-Tropsch Synthesis Catalysts over Spherical Mesoporous Carbon with Developed Porosity. Chem. Eng. J. 2018, 334, 714724. 28


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(18) Sun, Z.; Sun, B.; Qiao, M.; Wei, J.; Yue, Q.; Wang, C.; Deng, Y.; Kaliaguine, S.; Zhao, D. A General Chelate-assisted Co-assembly to Metallic Nanoparticles-incorporated Ordered Mesoporous Carbon Catalysts for Fischer-Tropsch Synthesis. J. Am. Chem. Soc. 2012, 134, 17653-60. (19) Chen, F.; Jin, W.; Cheng,D.; Zhan, Z.; Lin, Y. Fabrication of AC@ZSM-5 Coreshell Particles and their Performance in Fischer–Tropsch Synthesis. J. Chem. Technol. Biot. 2013, 88, 2133-2140. (20) Díaz, J. A.; Akhavan, H.; Romero, A.; Garcia-Minguillan, A. M.; Romero, R.; Giroir-Fendler, A.; Valverde, J. L. Cobalt and Iron Supported on Carbon Nanofibers as Catalysts for Fischer–Tropsch Synthesis. Fuel Process. Technol. 2014, 128, 417-424. (21) Xiong, H.; Motchelaho, M. A. M.; Moyo, M.; Jewell, L. L.; Coville, N. J. Correlating the Preparation and Performance of Cobalt Catalysts Supported on Carbon Nanotubes and Carbon Spheres in the Fischer–Tropsch Synthesis. J. Catal. 2011, 278, 2640. (22) Karimi, A.; Nasernejad, B.; Rashidi, A. M.; Tavasoli, A.; Pourkhalil, M. Functional Group Effect on Carbon Nanotube (CNT)-supported Cobalt Catalysts in Fischer–Tropsch Synthesis Activity, Selectivity and Stability. Fuel 2014, 117, 1045-1051. (23) Yang, Y.; Jia, L.; Meng, Y.; Hou, B.; Li, D.; Sun, Y. Fischer–Tropsch Synthesis over Ordered Mesoporous Carbon Supported Cobalt Catalysts: The Role of Amount of Carbon Precursor in Catalytic Performance. Catal. Lett. 2011, 142, 195-204. 29



(24) Yang, Y.; Jia, L.; Hou, B.; Li, D.; Wang, J.; Sun, Y. The Oxidizing Pretreatmentmediated Autoreduction Behaviour of Cobalt Nanoparticles Supported on Ordered Mesoporous Carbon for Fischer–Tropsch Synthesis. Catal. Sci. Technol. 2014, 4, 717-728. (25) Yang, Y.; Jia, L.; Hou, B.; Li, D.; Wang, J.; Sun, Y. The Effect of Nitrogen on the Autoreduction of Cobalt Nanoparticles Supported on Nitrogen-Doped Ordered Mesoporous Carbon for the Fischer-Tropsch Synthesis. ChemCatChem 2014, 6, 319-327. (26) Zhao, D.; Feng, J.; Huo, Q.; N, Melosh.; Glenn H. Fredrickson.; Bradley F. Chmelka.; Galen D. Stucky. Triblock Copolymer Syntheses of Mesoporous Silica with Periodic 50 to 300 Angstrom Pores. Science 1998, 279, 548-552. (27) Zeng, J.; Francia, C.; Dumitrescu, M. A.; Monteverde Videla, A. H. A.; Ijeri, V. S.; Specchia, S.; Spinelli, P. Electrochemical Performance of Pt-Based Catalysts Supported on Different Ordered Mesoporous Carbons (Pt/OMCs) for Oxygen Reduction Reaction. Ind. Eng. Chem. Res. 2011, 51, 7500-7509. (28) Song, D.; Li, J. Effect of Catalyst Pore Size on the Catalytic Performance of Silica Supported Cobalt Fischer–Tropsch Catalysts. J. Mol. Catal. A-Chem. 2006, 247, 206-212. (29) Overett, M. J.; Hill, R. O.; Moss, J. R. Organometallic Chemistry and Surface Science: Mechanistic Models for the Fischer–Tropsch Synthesis. Coordin. Chem. Rev. 2000, 206-207, 581-605. (30) Ha, K. S.; Kwak, G.; Jun, K. W.; Hwang, J.; Lee, J. Ordered Mesoporous Carbon Nanochannel Reactors for High-performance Fischer-Tropsch Synthesis. Chem. Commun. 30


Page 30 of 35

Page 31 of 35 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(Camb) 2013, 49, 5141-5143. (31) Liu, G.; Zheng, S.; Yin, D.; Xu, Z.; Fan, J.; Jiang, F. Adsorption of Aqueous Alkylphenol Ethoxylate Surfactants by Mesoporous Carbon CMK-3. J. Colloid Interf. Sci. 2006, 302, 47-53. (32) Fu, T.; Jiang, Y.; Lv, J.; Li, Z. Effect of Carbon Support on Fischer–Tropsch Synthesis Activity and Product Distribution over Co-based Catalysts. Fuel Process. Technol. 2013, 110, 141-149. (33) Osakoo, N.; Henkel, R.; Loiha, S.; Roessner, F.; Wittayakun, J. Comparison of PdCo/SBA-15 Prepared by Co-impregnation and Sequential Impregnation for Fischer– Tropsch Synthesis. Catal. Commun. 2015, 66, 73-78. (34) Li, H.; Hou, B.; Wang, J.; Huang, X.; Chen, C.; Ma, Z.; Cui, J.; Jia, L.; Sun, D.; Li, D. Effect of Hierarchical Meso–macroporous Structures on the Catalytic Performance of Silica Supported Cobalt Catalysts for Fischer–Tropsch Synthesis. Catal. Sci. Technol. 2017, 7, 3812-3822. (35) Zhu, Z.; Lu, G.; Zhang, Z.; Guo, Y.; Guo, Y.; Wang, Y. Highly Active and Stable Co3O4/ZSM-5 Catalyst for Propane Oxidation: Effect of the Preparation Method. ACS Catal. 2013, 3, 1154-1164. (36) Hou, X.; Wang, Y.; Zhao, Y. Effect of CeO2 Doping on Structure and Catalytic Performance of Co3O4 Catalyst for Low-Temperature CO Oxidation. Catal. Lett. 2008, 123, 321-326. 31



(37) Yung, M.; Holmgreen, E.; Ozkan, U. Cobalt-based Catalysts Supported on Titania and Zirconia for the Oxidation of Nitric Oxide to Nitrogen Dioxide. J. Catal. 2007, 247, 356-367. (38) Li, B.; Zhu, Y.; Jin, X. Synthesis of Cobalt-containing Mesoporous Catalysts Using the Ultrasonic-assisted “pH-adjusting” Method: Importance of Cobalt Species in Styrene Oxidation. J. Solid State Chem. 2015, 221, 230-239. (39) Tang, Q.; Zhang, Q.; Wu, H.; Wang, Y. Epoxidation of Styrene with Molecular Oxygen Catalyzed by Cobalt(II)-containing Molecular Sieves. J. Catal. 2005, 230, 384397. (40) Bechara, R.; Balloy, D.; Dauphin, J.; Grimblot, J. Influence of the Characteristics of γ-Aluminas on the Dispersion and the Reducibility of supported Cobalt Catalysts. Chem. Mater. 1999, 11, 1703-1711. (41) Guczi, L.; Bazin, D. Structure and Selectivity of Metal Catalysts: Revisiting Bimetallic Zeolite Systems. Appl. Catal., A 1999, 188, 163-174. (42) Verberckmoes, A. A.; Weckhuysen, B. M.; Schoonheydt, R. A. Spectroscopy and Coordination Chemistry of Cobalt in Molecular Sieves. Micropor. Mesopor. Mat. 1998, 22, 165-178. (43) Cui, H.; Zhang, Y.; Qiu, Z.; Zhao, L.; Zhu, Y. Synthesis and Characterization of Cobalt-substituted SBA-15 and its High Activity in Epoxidation of Styrene with Molecular Oxygen. Appl. Catal., B 2010, 101, 45-53. 32


Page 32 of 35

Page 33 of 35 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(44) Tao, C.; Li, J.; Liew, K. Y. Effect of the Pore Size of Co/SBA-15 Isomorphically Substituted with Zirconium on its Catalytic Performance in Fischer-Tropsch Synthesis. Sci. China Chem. 2010, 53, 2551-2559. (45) Hong, J.; Chu, W.; Chernavskii, P. A.; Khodakov, A. Y. Cobalt Species and Cobaltsupport Interaction in Glow Discharge Plasma-assisted Fischer–Tropsch Catalysts. J. Catal. 2010, 273, 9-17. (46) Karandikar, P. R.; Park, J.-Y.; Lee, Y.-J.; Jun, K.-W.; Ha, K.-S.; Kwak, G. J.; Park, H.-G.; Cheon, J. Y. Fischer-Tropsch Synthesis Over Cobalt Supported On SilicaIncorporated Mesoporous Carbon. ChemCatChem 2013, 5, 1461-1471. (47) Cheng, K.; Subramanian, V.; Carvalho, A.; Ordomsky, V. V.; Wang, Y.; Khodakov, A. Y. The Role of Carbon Pre-coating for the Synthesis of Highly Efficient Cobalt Catalysts for Fischer–Tropsch Synthesis. J. Catal. 2016, 337, 260-271. (48) Lu, Y.; Zhou, P.; Han, J.; Yu, F. Fischer–Tropsch Synthesis of Liquid Hydrocarbons over Mesoporous SBA-15 Supported Cobalt Catalysts. RSC Adv. 2015, 5, 59792-59803. (49) Li, Z.; Wu, J.; Yu, J.; Han, D.; Wu, L.; Li, J. Effect of Incorporation Manner of Zr on the Co/SBA-15 Catalyst for the Fischer–Tropsch Synthesis. J. Mol. Catal. A-Chem. 2016, 424, 384-392. (50) Den Breejen, J. P.; Radstake, P. B.; Bezemer, G. L.; Bitter, J. H.; Frøseth, V.; Holmen, A.; De Jong, K. P. On the Origin of the Cobalt Particle size Effects in Fischer-Tropsch Catalysis. J. Am. Chem. Soc. 2009, 131, 7197. 33



(51) Fu, T.; Lv, J.; Li, Z. Effect of Carbon Porosity and Cobalt Particle Size on the Catalytic Performance of Carbon Supported Cobalt Fischer–Tropsch Catalysts. Ind. Eng. Chem. Res. 2014, 53, 1342-1350.

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Graphic abstract


Co-Based Catalysts Supported on Silica and Carbon Materials: Effect

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