Unraveling the role of Ni13 catalyst supported on ZrO2 for CH4 dehydrogenation: The d-band electron reservoir

ZHI Cui-mei; YANG Rui-hong; ZHOU Chang-yu; WANG Gui-ru; DING Jia-ying; YANG Wen

doi:10.1016/S1872-5813(21)60184-6

Volume 50 Issue 5

May 2022

Turn off MathJax

Article Contents

Article Navigation > Journal of Fuel Chemistry and Technology > 2022 > 50(5): 601-610

ZHI Cui-mei, YANG Rui-hong, ZHOU Chang-yu, WANG Gui-ru, DING Jia-ying, YANG Wen. Unraveling the role of Ni13 catalyst supported on ZrO2 for CH4 dehydrogenation: The d-band electron reservoir[J]. Journal of Fuel Chemistry and Technology, 2022, 50(5): 601-610. doi: 10.1016/S1872-5813(21)60184-6

Citation:

ZHI Cui-mei, YANG Rui-hong, ZHOU Chang-yu, WANG Gui-ru, DING Jia-ying, YANG Wen. Unraveling the role of Ni₁₃ catalyst supported on ZrO₂ for CH₄ dehydrogenation: The d-band electron reservoir[J]. Journal of Fuel Chemistry and Technology, 2022, 50(5): 601-610. doi: 10.1016/S1872-5813(21)60184-6

Citation:

PDF( 1289 KB)

Unraveling the role of Ni₁₃ catalyst supported on ZrO₂ for CH₄ dehydrogenation: The d-band electron reservoir

doi: 10.1016/S1872-5813(21)60184-6

1.
College of Chemical and Biological Engineering, Shanxi Key Laboratory of High Value Utilization of Coal Gangue, Taiyuan University of Science and Technology, Taiyuan 030024, China
2.
Shanxi Health Vocational College, Taiyuan 030012, China
3.
Shanxi Key Laboratory of Metal Forming Theory and Technology, School of Material Science and Engineering, Taiyuan University of Science and Technology, Taiyuan 030024, China

Funds: The project was supported by the National Natural Science Foundation of China (51871158), the Fundamental Research Program of Shanxi Province (201901D111273), the Innovation and Entrepreneurship Training Program for College Students of Shanxi Province (20210491), Scientific and technological innovation project of colleges and universities in Shanxi Province (2020L0353), the PhD Startup Fund of Taiyuan University of Science and Technology (20182003).

More Information

Corresponding author: E-mail: 201821060219@stu.tyust.edu.cn; yangwen@tyust.edu.cn
Received Date: 2021-10-12
Accepted Date: 2021-12-03
Rev Recd Date: 2021-12-03

Available Online: 2021-12-13

Publish Date: 2022-05-24

Abstract

Abstract

The activation of C−H bonds of CH₄ is a key step for the conversion of methane to chemical commodities. Loading Ni onto ZrO₂ is regarded as a relatively efficient way to harness the beneficial electronic property and the fine dispersion of the Ni catalyst for CH₄ dissociation. Herein we demonstrate the crucial role of Ni₁₃ catalyst supported on ZrO₂ for the dissociation of CH₄. The density functional theory (DFT) results show that the ZrO₂ supported Ni₁₃ stabilizes all species better and facilitates CH₄ activation. The stepwise dehydrogenations of CH₄ on Ni₁₃-ZrO₂(111) exhibits longer C−H bond lengths of ISs , lower E_a, and smaller displacements between the detaching H and the remaining CH_x fragment in TSs . In addition, they are also thermodynamically more feasible. However, without the ZrO₂ support on Ni₁₃, the opposite results are obtained. Consequently, the ZrO₂ modified Ni₁₃ is more superior to the original Ni₁₃ in CH₄ dehydrogenation. The electronic analysis combining DFT calculations confirmed that the larger overlap between C 2p and Ni 3d, and the electron transfer of Ni→C cause the weaker C 2p−H 1s hybridization. In addition, the reduction of electron transfer of H→C leads to a stronger interaction between Ni and C along with a weak C−H bond. Hence, the ZrO₂support serves as the d-band electron reservoir at Ni₁₃ and it is benefit to the activation of C−H bonds in CH₄ dehydrogenation.
- CH₄ dehydrogenation,
- Ni₁₃ catalyst,
- ZrO₂ support,
- d-band electron,
- electron transfer

FullText(HTML)

References(48)

References

[1]	STOLAROFF J K, BHATTACHARYYA S, SMITH C A, BOURCIER W L, CAMERON-SMITH P J, AINES R D. Review of methane mitigation technologies with application to rapid release of methane from the arctic[J]. Environ Sci Technol,2012,46(12):6455−6469. doi: 10.1021/es204686w
[2]	CABALLERO A, PÉREZ P J. Methane as raw material in synthetic chemistry: The final frontier[J]. Chem Soc Rev,2013,42(23):8809−8820. doi: 10.1039/c3cs60120j
[3]	GROOTEL P W V, SANTEN R A V, HENSEN E J M. Methane dissociation on high and low indices Rh surfaces[J]. J Phys Chem C,2011,115(26):13027−13034. doi: 10.1021/jp2033774
[4]	LI B, METIU H. Dissociation of methane on La₂O₃ surfaces doped with Cu, Mg, or Zn[J]. J Phys Chem C,2011,115(37):18239−18246. doi: 10.1021/jp2049603
[5]	ZHANG T Y, HOLIHARIMANANA D, YANG X F, GE Q F. DFT study of methane activation and coupling on the (0001) and (112̅0) surfaces of α-WC[J]. J Phys Chem C,2020,124(49):26722−26729. doi: 10.1021/acs.jpcc.0c06928
[6]	ROY G, CHATTOPADHYAY A P. Dissociation of methane on Ni₄ cluster-A DFT study[J]. Comput Theor Chem,2017,1106:7−14. doi: 10.1016/j.comptc.2017.02.030
[7]	LI J D, CROISET E, RICARDEZ-SANDOVAL L. Methane dissociation on Ni(100), Ni(111), and Ni(553): A comparative density functional theory study[J]. J Mol Catal A-Chem,2012,365:103−114. doi: 10.1016/j.molcata.2012.08.016
[8]	LI J D, CROISET E, RICARDEZ-SANDOVAL L. Effect of carbon on the Ni catalyzed methane cracking reaction: A DFT study[J]. Appl Surf Sci,2014,311:435−442. doi: 10.1016/j.apsusc.2014.05.081
[9]	VASILIADES M A, DJINOVIĆ P, PINTAR A, KOVAČ J, EFSTATHIOU A M. The effect of CeO₂-ZrO₂ structural differences on the origin and reactivity of carbon formed during methane dry reforming over NiCo/CeO₂-ZrO₂ catalysts studied by transient techniques[J]. Catal Sci Technol,2017,7:5422−5434. doi: 10.1039/C7CY01009E
[10]	ZHANG S S, YING M, YU J, ZHAN W C, WANG L, GUO Y, GUO Y L. Ni_xAl₁O_2-δ mesoporous catalysts for dry reforming of methane: The special role of NiAl₂O₄ spinel phase and its reaction mechanism[J]. Appl Catal B: Environ,2021,291:120074. doi: 10.1016/j.apcatb.2021.120074
[11]	ZHANG L, WANG X G, SHANG X F, TAN M W, DING W Z, LU X G. Carbon dioxide reforming of methane over mesoporous nickel aluminate/γ-alumina composites[J]. J Energy Chem,2017,26(1):93−100. doi: 10.1016/j.jechem.2016.08.001
[12]	WANG Y, YAO L, WANG Y N, WANG S H, ZHAO Q, MAO D H, HU C W. Low-temperature catalytic CO₂ dry reforming of methane on Ni-Si/ZrO₂ catalyst[J]. ACS Catal,2018,8(7):6495−6506. doi: 10.1021/acscatal.8b00584
[13]	HAN J W, PARK J S, CHOI M S, LEE H. Uncoupling the size and support effects of Ni catalysts for dry reforming of methane[J]. Appl Catal B: Environ,2017,203:625−632. doi: 10.1016/j.apcatb.2016.10.069
[14]	BAUDOUIN D, RODEMERCK U, KRUMEICH F, MALLMANN A D, SZETO K C, MÉNARD H, VEYRE L, CANDY J P, WEBB P B, THIEULEUX C, COPÉRET C. Particle size effect in the low temperature reforming of methane by carbon dioxide on silica-supported Ni nanoparticles[J]. J Catal,2013,297:27−34. doi: 10.1016/j.jcat.2012.09.011
[15]	CUI Y H, XU H Y, GE Q J, WANG Y Z, HOU S F, LI W Z. Structure sensitive dissociation of CH₄ on Ni/α-Al₂O₃: Ni nano-scale particles linearly compensate the E_a and ln A for the CH₄ pulse kinetics[J]. J Mol Catal A-Chem,2006,249(1/2):53−59. doi: 10.1016/j.molcata.2006.01.009
[16]	YAN X L, HU T, LIU P, LI S, ZHAO B R, ZHANG Q, JIAO W Y, CHEN S, WANG P F, LU JJ, FAN L M, DENG X N, PAN Y X. Highly efficient and stable Ni/CeO₂-SiO₂ catalyst for dry reforming of methane: Effect of interfacial structure of Ni/CeO₂ on SiO₂[J]. Appl Catal B Environ,2019,246:221−231. doi: 10.1016/j.apcatb.2019.01.070
[17]	KAMBOLIS A, MATRALIS H, TROVARELLI A, PAPADOPOULOU C. Ni/CeO₂-ZrO₂ catalysts for the dry reforming of methane[J]. Appl Catal A: Gen,2010,377(1/2):16−26. doi: 10.1016/j.apcata.2010.01.013
[18]	DJINOVIĆ P, ČRNIVEC I G O, ERJAVEC B, PINTAR A. Influence of active metal loading and oxygen mobility on coke-free dry reforming of Ni-Co bimetallic catalysts[J]. Appl Catal B: Environ,2012,125:259−270. doi: 10.1016/j.apcatb.2012.05.049
[19]	YAO L, SHI J, XU H L, SHEN W, HU C W. Low-temperature CO₂ reforming of methane on Zr-promoted Ni/SiO₂ catalyst[J]. Fuel Process Technol,2016,144:1−7. doi: 10.1016/j.fuproc.2015.12.009
[20]	ZHANG M, ZHANG J F, ZHOU Z L, CHEN S Y, ZHANG T, SONG F E, ZHANG Q D, TSUBAKI N, TAN Y S, HAN Y Z. Effects of the surface adsorbed oxygen species tuned by rare-earth metal doping on dry reforming of methane over Ni/ZrO₂ catalyst[J]. Appl Catal B: Environ,2020,264:118522. doi: 10.1016/j.apcatb.2019.118522
[21]	DĘBEK R, GALVEZ M E, LAUNAY F, MOTAK M, GRZYBEK T, COSTA P D. Low temperature dry methane reforming over Ce, Zr and CeZr promoted Ni-Mg-Al hydrotalcite-derived catalysts[J]. Int J Hydrogen Energy,2016,41(27):11616−11623. doi: 10.1016/j.ijhydene.2016.02.074
[22]	YAO L, WANG Y, SHI J, XU H L, SHEN W, HU C W. The influence of reduction temperature on the performance of ZrO_x/Ni-MnO_x/SiO₂ catalyst for low-temperature CO₂ reforming of methane[J]. Catal Today,2017,281(1):259−267.
[23]	ZHANG S H, MURATSUGU S, ISHIGURO N, TADA M. Ceria-doped Ni/SBA-16 catalysts for dry reforming of methane[J]. ACS Catal,2013,3(8):1855−1864. doi: 10.1021/cs400159w
[24]	LI K, PEI C L, LI X Y, CHEN S, ZHANG X H, LIU R, GONG J L. Dry reforming of methane over La₂O₂CO₃-modified Ni/Al₂O₃ catalysts with moderate metal support interaction[J]. Appl Catal B Environ,2020,264:118448. doi: 10.1016/j.apcatb.2019.118448
[25]	KE Q, KANG L M, CHEN X, WU Y. DFT study of CO₂ catalytic conversion by H₂ over Ni₁₃ cluster[J]. J Chem Sci,2020,132(1):151. doi: 10.1007/s12039-020-01857-3
[26]	YILMAZER N D, FELLAH M F, ONAL I. A DFT study of ethylene hydrogenation reaction mechanisms on Ni₁₃ nanocluster[J]. Top Catal,2013,56(9/10):789−793. doi: 10.1007/s11244-013-0043-0
[27]	RUSINA G G, BORISOVA S D, CHULKOV E V. Structure and atomic vibrations in bimetallic Ni_13-nAl_n clusters[J]. JETP Lett,2015,101(7):474−480. doi: 10.1134/S0021364015070139
[28]	BANERJEE R, DATTA S, MOOKERJEE A. Structure, reactivity and electronic properties of M_n doped Ni₁₃ clusters[J]. Phys B,2013,419(21):86−89.
[29]	CHEN S J, CHEN X, ZHANG H. Probing the activity of Ni₁₃, Cu₁₃ and Ni₁₂Cu clusters towards the ammonia decomposition reaction by density functional theory[J]. J Mater Sci,2016,52(6):3162−3168.
[30]	YILMAZER N D, FELLAH M F, ONAL I. A density functional theory study of ethylene adsorption on Ni₁₀(111), Ni₁₃(100) and Ni₁₀(110) surface cluster models and Ni₁₃ nanocluster[J]. Appl Surf Sci,2010,256(16):5088−5093. doi: 10.1016/j.apsusc.2010.03.067
[31]	YAO Y H, GU X, JI M, GONG X G, WANG D S. Structures and magnetic moments of Ni_n (n=10~60) clusters[J]. Phys Lett A,2007,360(4/5):629−631. doi: 10.1016/j.physleta.2006.08.059
[32]	LIU B, LUSK M T, ELY J F. Influence of nickel catalyst geometry on the dissociation barriers of H₂ and CH₄: Ni₁₃ versus Ni(111)[J]. J Phys Chem C,2009,113(31):13715−13722. doi: 10.1021/jp9003196
[33]	GRIGORYAN V G, SPRINGBORG M. A theoretical study of the structure of Ni clusters (Ni_N)[J]. Phys Chem Chem Phys,2001,3(23):5135−5139. doi: 10.1039/b105831m
[34]	MORTENSEN J J, HANSEN L B, JACOBSEN K W. Real-space grid implementation of the projector augmented wave method[J]. Phys Rev B,2005,71:035109. doi: 10.1103/PhysRevB.71.035109
[35]	REXER E F, JELLINEK J, KRISSINEL E B, PARK E K, RILEY S J. Theoretical and experimental studies of the structures of 12-, 13-, and 14-atom bimetallic nickel/aluminum clusters[J]. J Chem Phys,2002,117(1):82−94. doi: 10.1063/1.1481386
[36]	STEFANOVICH E V, SHLUGER A L, CATLOW C R A. Theoretical study of the stabilization of cubic-phase ZrO₂ by impurities[J]. Phys Rev B,1994,49(17):11560−11571. doi: 10.1103/PhysRevB.49.11560
[37]	EREMEEV S V, NEMIROVICH-DANCHENKO L Y, KUL′KOVA S E. Effect of oxygen vacancies on adhesion at the Nb/Al₂O₃ and Ni/ZrO₂ interfaces[J]. Phys Solid State,2008,50:543−552. doi: 10.1134/S1063783408030256
[38]	BELTRÁN J I, GALLEGO S, CERDÁJ, MOYA J S, MUÑOZ M C. Bond formation at the Ni/ZrO₂ interface[J]. Phys Rev B,2003,68(7):075401. doi: 10.1103/PhysRevB.68.075401
[39]	ZHANG M, ZIJLSTRA B, FILOT IAW, LI F, WANG HO, LI J D, HENSEN EJM. A theoretical study of the reverse water-gas shift reaction on Ni(111) and Ni(311) surfaces[J]. Can J Chem Eng,2020,98(3):740−748. doi: 10.1002/cjce.23655
[40]	MONKHORST H J, PACK J D. Special points for brillouin-zone integrations[J]. Phys Rev B,1976,13(12):5188−5192. doi: 10.1103/PhysRevB.13.5188
[41]	ZHI C M, YANG W. Improvement of Mo-doping on Sulfur-poisoning of Ni catalyst: Activity and selectivity to CO methanation[J]. Comput Theor Chem,2021,1197:113140. doi: 10.1016/j.comptc.2020.113140
[42]	KAPUR N, HYUN J, SHAN B, NICHOLAS J B, CHO K. Ab initio study of CO hydrogenation to oxygenates on reduced Rh terraces and stepped surfaces[J]. J Phys Chem C,2010,114(22):10171−10182. doi: 10.1021/jp911903u
[43]	AN W, CHEN X C, TURNER C H. First-principles study of methane dehydrogenation on a bimetallic Cu/Ni(111) surface[J]. J Chem Phys,2009,131(17):174702. doi: 10.1063/1.3254383
[44]	OU Z L, RAN J Y, NIU J T, ZHANG Z H, DENG T, HE Z Q, QIN C L. Effect of active site and charge transfer on methane dehydrogenation over different Co doped Ni surfaces by density functional theory[J]. Int J Hydrogen Energy,2020,45(56):31849−31862. doi: 10.1016/j.ijhydene.2020.08.187
[45]	PETERSSON G A, TENSFELDT T G, MONTGOMERY JR J A. Vinylidene and the hammond postulate[J]. J Am Chem Soc,1992,114:6133−6138. doi: 10.1021/ja00041a034
[46]	CHEN Z X, ALEKSANDROV H A, BASARAN D, RÖSCH N. Transformations of ethylene on the Pd(111) surface: A density functional study[J]. J Phys Chem C,2010,114(41):17683−17692. doi: 10.1021/jp104949w
[47]	ZHAO Z J, CHIU C C, GONG J L. Molecular understandings on the activation of light hydrocarbons over heterogeneous catalysts[J]. Chem Sci,2015,6(8):4403−4425. doi: 10.1039/C5SC01227A
[48]	KHETTAL H, HAROUN M F, BOUKELKOUL M. Theoretical study of CH₄ adsorption and dissociation on W-Cu(100) surface[J]. Comput Theor Chem,2020,1186:112890. doi: 10.1016/j.comptc.2020.112890