Catalysis of semihydrogenation of acetylene to ethylene: current trends, challenges, and outlook

Abstract

Ethylene is an important feedstock for various industrial processes, particularly in the polymer industry. Unfortunately, during naphtha cracking to produce ethylene, there are instances of acetylene presence in the product stream, which poisons the Ziegler–Natta polymerization catalysts. Thus, appropriate process modification, optimization, and in particular, catalyst design are essential to ensure the production of highly pure ethylene that is suitable as a feedstock in polymerization reactions. Accordingly, carefully selected process parameters and the application of various catalyst systems have been optimized for this purpose. This review provides a holistic view of the recent reports on the selective hydrogenation of acetylene. Previously published reviews were limited to Pd catalysts. However, effective new metal and non-metal catalysts have been explored for selective acetylene hydrogenation. Updates on this recent progress and more comprehensive computational studies that are now available for the reaction are described herein. In addition to the favored Pd catalysts, other catalyst systems including mono, bimetallic, trimetallic, and ionic catalysts are presented. The specific role(s) that each process parameter plays to achieve high acetylene conversion and ethylene selectivity is discussed. Attempts have been made to elucidate the possible catalyst deactivation mechanisms involved in the reaction. Extensive reports suggest that acetylene adsorption occurs through an active single-site mechanism rather than via dual active sites. An increase in the reaction temperature affords high acetylene conversion and ethylene selectivity to obtain reactant streams free of ethylene. Conflicting findings to this trend have reported the presence of ethylene in the feed stream. This review will serve as a useful resource of condensed information for researchers in the field of acetylene-selective hydrogenation.

Graphical abstract

Keywords

selectivity / hydrogenation / acetylene / ethylene / palladium

References

[1] Barazandeh K, Dehghani O, Hamidi M, Aryafard E, Rahimpour M R. Investigation of coil outlet temperature effect on the performance of naphtha cracking furnace. Chemical Engineering Research & Design, 2015, 94(14): 307–316

[2] Dehghani O, Rahimpour M R, Shariati A. An experimental approach on industrial Pd-Ag supported α-Al₂O₃ catalyst used in acetylene hydrogenation process: mechanism, kinetic and catalyst decay. Processes (Basel, Switzerland), 2019, 7(3): 136–157

[3] Benavidez A D, Burton P D, Nogales J L, Jenkins A R, Ivanov S A, Miller J T, Karim A M, Datye A K. Improved selectivity of carbon-supported palladium catalysts for the hydrogenation of acetylene in excess ethylene. Applied Catalysis A, General, 2014, 482: 108–115

[4] He Y, Liang L, Liu Y, Feng J, Ma C, Li D. Partial hydrogenation of acetylene using highly stable dispersed bimetallic Pd-Ga/MgO-Al₂O₃ catalyst. Journal of Catalysis, 2014, 309: 166–173

[5] Molnár Á, Sárkány A, Varga M. Hydrogenation of carbon-carbon multiple bonds: chemo-, regio- and stereo-selectivity. Journal of Molecular Catalysis A Chemical, 2001, 173(1–2): 185–221

[6] Urmès C, Schweitzer J M, Cabiac A, Schuurman Y. Kinetic study of the selective hydrogenation of acetylene over supported palladium under tail-end conditions. Catalysts, 2019, 9(2): 180–192

[7] McCue A J, Anderson J A. Recent advances in selective acetylene hydrogenation using palladium containing catalysts. Frontiers of Chemical Science and Engineering, 2015, 9(2): 142–153

[8] Zhou H, Yang X, Li L, Liu X, Huang Y, Pan X, Wang A, Li J, Zhang T. PdZn intermetallic nanostructure with Pd-Zn-Pd ensembles for highly active and chemoselective semi-hydrogenation of acetylene. ACS Catalysis, 2016, 6(2): 1054–1061

[9] Liu Y, McCue A J, Miao C, Feng J, Li D, Anderson J A. Palladium phosphide nanoparticles as highly selective catalysts for the selective hydrogenation of acetylene. Journal of Catalysis, 2018, 364: 406–414

[10] Gärtner C A, van Veen A C, Lercher J A. Oxidative dehydrogenation of ethane: common principles and mechanistic aspects. ChemCatChem, 2013, 5(11): 3196–3217

[11] Esmaeili E, Mortazavi Y, Khodadadi A A, Rashidi A M, Rashidzadeh M. The role of tin-promoted Pd/MWNTs via the management of carbonaceous species in selective hydrogenation of high concentration acetylene. Applied Surface Science, 2012, 263: 513–522

[12] Ravanchi M T, Sahebdelfar S, Komeili S. Acetylene selective hydrogenation: a technical review on catalytic aspects. Reviews in Chemical Engineering, 2018, 34(2): 215–237

[13] Ayodele O B, Cai R, Wang J, Ziouani Y, Liang Z, Chiara Spadaro M, Kovnir K, Arbiol J, Akola J, Palmer R, . Synergistic computational-experimental discovery of highly selective PtCu nanocluster catalysts for acetylene semihydrogenation. ACS Catalysis, 2019, 10(1): 451–457

[14] Zhang S, Chen C Y, Jang B W L, Zhu A M. Radio-frequency H₂ plasma treatment of AuPd/TiO₂ catalyst for selective hydrogenation of acetylene in excess ethylene. Catalysis Today, 2015, 256: 161–169

[15] Gulyaeva Y K, Kaichev V V, Zaikovskii V I, Kovalyov E V, Suknev A P, Bal’zhinimaev B S. Selective hydrogenation of acetylene over novel Pd/fiberglass catalysts. Catalysis Today, 2015, 245: 139–146

[16] Komeili S, Takht Ravanchi M, Rahimi Fard M, Taeb A. Effect of Ni-modified alpha alumina on the textural properties as a catalyst support. In 8th International Chemical Engineering Congress (IChEC 2014), Kish Island, Iran. 2014

[17] McKenna F, Mantarosie L, Wells R, Hardacre C, Anderson J. Selective hydrogenation of acetylene in ethylene rich feed streams at high pressure over ligand modified Pd/TiO₂. Catalysis Science & Technology, 2012, 2(3): 632–638

[18] Yang B, Burch R, Hardacre C, Headdock G, Hu P. Influence of surface structures, subsurface carbon and hydrogen, and surface alloying on the activity and selectivity of acetylene hydrogenation on Pd surfaces: a density functional theory study. Journal of Catalysis, 2013, 305: 264–276

[19] Hu M, Wang X. Effect of N₃^– species on selective acetylene hydrogenation over Pd/SAC catalysts. Catalysis Today, 2016, 263: 98–104

[20] Crespo-Quesada M, Yoon S, Jin M, Prestianni A, Cortese R, Cárdenas-Lizana F, Duca D, Weidenkaff A, Kiwi-Minsker L. Shape-dependence of Pd nanocrystal carburization during acetylene hydrogenation. Journal of Physical Chemistry C, 2015, 119(2): 1101–1107

[21] Jin Q, He Y, Miao M, Guan C, Du Y, Feng J, Li D. Highly selective and stable PdNi catalyst derived from layered double hydroxides for partial hydrogenation of acetylene. Applied Catalysis A, General, 2015, 500: 3–11

[22] Kim W J, Moon S H. Modified Pd catalysts for the selective hydrogenation of acetylene. Catalysis Today, 2012, 185(1): 2–16

[23] Jin Y, Datye A K, Rightor E, Gulotty R, Waterman W, Smith M, Holbrook M, Maj J, Blackson J. The influence of catalyst restructuring on the selective hydrogenation of acetylene to ethylene. Journal of Catalysis, 2001, 203(2): 292–306

[24] Mei D, Sheth P A, Neurock M, Smith C M. First-principles-based kinetic Monte Carlo simulation of the selective hydrogenation of acetylene over Pd (111). Journal of Catalysis, 2006, 242(1): 1–15

[25] Borodziński A, Bond G C. Selective hydrogenation of ethyne in ethene-rich streams on palladium catalysts. Part 1. Effect of changes to the catalyst during reaction. Catalysis Reviews, 2006, 48(02): 91–144

[26] Tejeda-Serrano M, Mon M, Ross B, Gonell F, Ferrando-Soria J, Corma A, Leyva-Pérez A, Armentano D, Pardo E. Isolated Fe(III)-O sites catalyze the hydrogenation of acetylene in ethylene flows under front-end industrial conditions. Journal of the American Chemical Society, 2018, 140(28): 8827–8832

[27] Albani D, Shahrokhi M, Chen Z, Mitchell S, Hauert R, López N, Pérez-Ramírez J. Selective ensembles in supported palladium sulfide nanoparticles for alkyne semi-hydrogenation. Nature Communications, 2018, 9(1): 2634–2644

[28] He Y, Liu Y, Yang P, Du Y, Feng J, Cao X, Yang J, Li D. Fabrication of a PdAg mesocrystal catalyst for the partial hydrogenation of acetylene. Journal of Catalysis, 2015, 330: 61–70

[29] Borodziński A, Bond G C. Selective hydrogenation of ethyne in ethene-rich streams on palladium catalysts, Part 2: Steady-state kinetics and effects of palladium particle size, carbon monoxide, and promoters. Catalysis Reviews, 2008, 50(3): 379–469

[30] Moses J M, Weiss A H, Matusek K, Guczi L. The effect of catalyst treatment on the selective hydrogenation of acetylene over palladium/alumina. Journal of Catalysis, 1984, 86(2): 417–426

[31] Backman A, Masel R. An electron energy-loss spectroscopy study analysis of the surface species formed during ethylene hydrogenation on Pt (111). Journal of Vacuum Science & Technology. A, Vacuum, Surfaces, and Films, 1991, 9(3): 1789–1792

[32] Shin E W, Kang J H, Kim W J, Park J D, Moon S H. Performance of Si-modified Pd catalyst in acetylene hydrogenation: the origin of the ethylene selectivity improvement. Applied Catalysis A, General, 2002, 223(1–2): 161–172

[33] Duca D, Frusteri F, Parmaliana A, Deganello G. Selective hydrogenation of acetylene in ethylene feedstocks on Pd catalysts. Applied Catalysis A, General, 1996, 146(2): 269–284

[34] Duca D, Arena F, Parmaliana A, Deganello G. Hydrogenation of acetylene in ethylene rich feedstocks: comparison between palladium catalysts supported on pumice and alumina. Applied Catalysis A, General, 1998, 172(2): 207–216

[35] Larsson M, Jansson J, Asplund S. Incorporation of deuterium in coke formed on an acetylene hydrogenation catalyst. Journal of Catalysis, 1996, 162(2): 365–367

[36] Larsson M, Jansson J, Asplund S. The role of coke in acetylene hydrogenation on Pd/α-Al₂O₃. Journal of Catalysis, 1998, 178(1): 49–57

[37] Park Y H, Price G L. Temperature-programmed-reaction study on the effect of carbon monoxide on the acetylene reaction over palladium/alumina. Industrial & Engineering Chemistry Research, 1991, 30(8): 1700–1707

[38] Park Y H, Price G L. Deuterium tracer study on the effect of carbon monoxide on the selective hydrogenation of acetylene over palladium/alumina. Industrial & Engineering Chemistry Research, 1991, 30(8): 1693–1699

[39] Sheth P A, Neurock M, Smith C M. A first-principles analysis of acetylene hydrogenation over Pd (111). Journal of Physical Chemistry B, 2003, 107(9): 2009–2017

[40] Borodziński A, Cybulski A. The kinetic model of hydrogenation of acetylene-ethylene mixtures over palladium surface covered by carbonaceous deposits. Applied Catalysis A, General, 2000, 198(1–2): 51–66

[41] Rose M, Mitsui T, Dunphy J, Borg A, Ogletree D, Salmeron M, Sautet P. Ordered structures of CO on Pd (111) studied by STM. Surface Science, 2002, 512(1–2): 48–60

[42] He Y, Fan J, Feng J, Luo C, Yang P, Li D. Pd nanoparticles on hydrotalcite as an efficient catalyst for partial hydrogenation of acetylene: effect of support acidic and basic properties. Journal of Catalysis, 2015, 331: 118–127

[43] Cao Y, Sui Z, Zhu Y, Zhou X, Chen D. Selective hydrogenation of acetylene over Pd-In/Al₂O₃ catalyst: promotional effect of indium and composition-dependent performance. ACS Catalysis, 2017, 7(11): 7835–7846

[44] Trimm D L, Liu I O, Cant N W. The effect of carbon monoxide on the oligomerization of acetylene in hydrogen over a Ni/SiO₂ catalyst. Journal of Molecular Catalysis A Chemical, 2009, 307(1–2): 13–20

[45] Bazzazzadegan H, Kazemeini M, Rashidi A. A high performance multi-walled carbon nanotube-supported palladium catalyst in selective hydrogenation of acetylene-ethylene mixtures. Applied Catalysis A, General, 2011, 399(1–2): 184–190

[46] Sarkany A, Horvath A, Beck A. Hydrogenation of acetylene over low loaded Pd and Pd-Au/SiO₂ catalysts. Applied Catalysis A, General, 2002, 229(1–2): 117–125

[47] Imbihl R, Behm R, Schlögl R. Bridging the pressure and material gap in heterogeneous catalysis. Physical Chemistry Chemical Physics, 2007, 9(27): 3459–3459

[48] Molero H, Bartlett B, Tysoe W. The hydrogenation of acetylene catalyzed by palladium: hydrogen pressure dependence. Journal of Catalysis, 1999, 181(1): 49–56

[49] Inoue Y, Yasumori I. Pressure jump and isotope replacement studies of acetylene hydrogenation on palladium surface. Journal of Physical Chemistry, 1971, 75(7): 880–887

[50] Riyapan S, Zhang Y, Wongkaew A, Pongthawornsakun B, Monnier J R, Panpranot J. Preparation of improved Ag-Pd/TiO₂ catalysts using the combined strong electrostatic adsorption and electroless deposition methods for the selective hydrogenation of acetylene. Catalysis Science & Technology, 2016, 6(14): 5608–5617

[51] Parker S F, Walker H C, Callear S K, Grünewald E, Petzold T, Wolf D, Möbus K, Adam J, Wieland S D, Jiménez-Ruiz M, . The effect of particle size, morphology and support on the formation of palladium hydride in commercial catalysts. Chemical Science (Cambridge), 2019, 10(2): 480–489

[52] Torres D, Cinquini F, Sautet P. Pressure and temperature effects on the formation of a Pd/C surface carbide: insights into the role of Pd/C as a selective catalytic state for the partial hydrogenation of acetylene. Journal of Physical Chemistry C, 2013, 117(21): 11059–11065

[53] Guo Z, Huang Q, Luo S, Chu W. Atmospheric discharge plasma enhanced preparation of Pd/TiO₂ catalysts for acetylene selective hydrogenation. Topics in Catalysis, 2017, 60(12–14): 1009–1015

[54] Guo Z, Liu Y, Liu Y, Chu W. Promising SiC support for Pd catalyst in selective hydrogenation of acetylene to ethylene. Applied Surface Science, 2018, 442: 736–741

[55] Hong J, Chu W, Chen M, Wang X, Zhang T. Preparation of novel titania supported palladium catalysts for selective hydrogenation of acetylene to ethylene. Catalysis Communications, 2007, 8(3): 593–597

[56] Gigola C, Aduriz H, Bodnariuk P. Particle size effect in the hydrogenation of acetylene under industrial conditions. Applied Catalysis, 1986, 27(1): 133–144

[57] Han Y, Peng D, Xu Z, Wan H, Zheng S, Zhu D. TiO₂ supported Pd@Ag as highly selective catalysts for hydrogenation of acetylene in excess ethylene. Chemical Communications, 2013, 49(75): 8350–8352

[58] Den Hartog A, Deng M, Jongerius F, Ponec V. Hydrogenation of acetylene over various group VIII metals: effect of particle size and carbonaceous deposits. Journal of Molecular Catalysis, 1990, 60(1): 99–108

[59] Huang F, Deng Y, Chen Y, Cai X, Peng M, Jia Z, Ren P, Xiao D, Wen X, Wang N, et al. Atomically dispersed Pd on nanodiamond/graphene hybrid for selective hydrogenation of acetylene. Journal of the American Chemical Society, 2018, 140(41): 13142–13146

[60] Armbrüster M, Kovnir K, Behrens M, Teschner D, Grin Y, Schlögl R. Pd-Ga intermetallic compounds as highly selective semihydrogenation catalysts. Journal of the American Chemical Society, 2010, 132(42): 14745–14747

[61] Zhou S, Shang L, Zhao Y, Shi R, Waterhouse G I, Huang Y C, Zheng L, Zhang T. Pd single-atom catalysts on nitrogen-doped graphene for the highly selective photothermal hydrogenation of acetylene to ethylene. Advanced Materials, 2019, 31(18): 1900509–1900515

[62] Cao Y, Fu W, Sui Z, Duan X, Chen D, Zhou X. Kinetics insights and active sites discrimination of Pd-catalyzed selective hydrogenation of acetylene. Industrial & Engineering Chemistry Research, 2019, 58(5): 1888–1895

[63] Komhom S, Mekasuwandumrong O, Praserthdam P, Panpranot J. Improvement of Pd/Al₂O₃ catalyst performance in selective acetylene hydrogenation using mixed phases Al₂O₃ support. Catalysis Communications, 2008, 10(1): 86–91

[64] McCue A J, McRitchie C J, Shepherd A M, Anderson J A. Cu/Al₂O₃ catalysts modified with Pd for selective acetylene hydrogenation. Journal of Catalysis, 2014, 319: 127–135

[65] McCue A J, Shepherd A M, Anderson J A. Optimisation of preparation method for Pd doped Cu/Al₂O₃ catalysts for selective acetylene hydrogenation. Catalysis Science & Technology, 2015, 5(5): 2880–2890

[66] Meunier F, Maffre M, Schuurman Y, Colussi S, Trovarelli A. Acetylene semi-hydrogenation over Pd-Zn/CeO₂: relevance of CO adsorption and methanation as descriptors of selectivity. Catalysis Communications, 2018, 105: 52–55

[67] Albani D, Capdevila-Cortada M, Vilé G, Mitchell S, Martin O, López N, Pérez-Ramírez J. Semihydrogenation of acetylene on indium oxide: proposed single-ensemble catalysis. Angewandte Chemie International Edition, 2017, 56(36): 10755–10760

[68] Kuhn M, Lucas M, Claus P. Long-time stability vs deactivation of Pd-Ag/Al₂O₃ egg-shell catalysts in selective hydrogenation of acetylene. Industrial & Engineering Chemistry Research, 2015, 54(26): 6683–6691

[69] Azizi Y, Petit C, Pitchon V. Formation of polymer-grade ethylene by selective hydrogenation of acetylene over Au/CeO₂ catalyst. Journal of Catalysis, 2008, 256(2): 338–344

[70] Jia J, Haraki K, Kondo J N, Domen K, Tamaru K. Selective hydrogenation of acetylene over Au/Al₂O₃ catalyst. Journal of Physical Chemistry B, 2000, 104(47): 11153–11156

[71] Kameoka S, Krajčí M, Tsai A P. Highly selective semi-hydrogenation of acetylene over porous gold with twin boundary defects. Applied Catalysis A, General, 2019, 569: 101–109

[72] Lee J W, Liu X, Mou C Y. Selective hydrogenation of acetylene over SBA-15 supported Au-Cu bimetallic catalysts. Journal of the Chinese Chemical Society (Taipei), 2013, 60(7): 907–914

[73] Liu X, Mou C Y, Lee S, Li Y, Secrest J, Jang B W L. Room temperature O₂ plasma treatment of SiO₂ supported Au catalysts for selective hydrogenation of acetylene in the presence of large excess of ethylene. Journal of Catalysis, 2012, 285(1): 152–159

[74] Peng S, Sun X, Sun L, Zhang M, Zheng Y, Su H, Qi C. Selective Hydrogenation of acetylene over gold nanoparticles supported on CeO₂ pretreated under different atmospheres. Catalysis Letters, 2019, 149(2): 465–472

[75] Pongthawornsakun B, Mekasuwandumrong O, Aires F J C S, Büchel R, Baiker A, Pratsinis S E, Panpranot J. Variability of particle configurations achievable by 2-nozzle flame syntheses of the Au-Pd-TiO₂ system and their catalytic behaviors in the selective hydrogenation of acetylene. Applied Catalysis A, General, 2018, 549: 1–7

[76] Zhang Y, Diao W, Williams C T, Monnier J R. Selective hydrogenation of acetylene in excess ethylene using Ag- and Au-Pd/SiO₂ bimetallic catalysts prepared by electroless deposition. Applied Catalysis A, General, 2014, 469: 419–426

[77] Rodríguez J, Marchi A, Borgna A, Monzón A. Effect of Zn content on catalytic activity and physicochemical properties of Ni-based catalysts for selective hydrogenation of acetylene. Journal of Catalysis, 1997, 171(1): 268–278

[78] Chen Y, Chen J. Selective hydrogenation of acetylene on SiO₂ supported Ni-In bimetallic catalysts: promotional effect of In. Applied Surface Science, 2016, 387: 16–27

[79] Riley C, De La Riva A, Zhou S, Wan Q, Peterson E, Artyushkova K, Farahani M D, Friedrich H B, Burkemper L, Atudorei N V, . Synthesis of nickel-doped ceria catalysts for selective acetylene hydrogenation. ChemCatChem, 2019, 11(5): 1526–1533

[80] Pei G X, Liu X Y, Wang A, Su Y, Li L, Zhang T. Selective hydrogenation of acetylene in an ethylene-rich stream over silica supported Ag-Ni bimetallic catalysts. Applied Catalysis A, General, 2017, 545: 90–96

[81] Trimm D L, Liu I O, Cant N W. The selective hydrogenation of acetylene over a Ni/SiO₂ catalyst in the presence and absence of carbon monoxide. Applied Catalysis A, General, 2010, 374(1–2): 58–64

[82] Wang L, Li F, Chen Y, Chen J. Selective hydrogenation of acetylene on SiO₂-supported Ni-Ga alloy and intermetallic compound. Journal of Energy Chemistry, 2019, 29: 40–49

[83] Matselko O, Zimmermann R R, Ormeci A, Burkhardt U, Gladyshevskii R, Grin Y, Armbrüster M. Revealing electronic influences in the semihydrogenation of acetylene. Journal of Physical Chemistry C, 2018, 122(38): 21891–21896

[84] Köhler D, Heise M, Baranov A I, Luo Y, Geiger D, Ruck M, Armbrüster M. Synthesis of BiRh nanoplates with superior catalytic performance in the semihydrogenation of acetylene. Chemistry of Materials, 2012, 24(9): 1639–1644

[85] Hu M, Zhang J, Zhu W, Chen Z, Gao X, Du X, Wan J, Zhou K, Chen C, Li Y. 50 ppm of Pd dispersed on Ni(OH)₂ nanosheets catalyzing semi-hydrogenation of acetylene with high activity and selectivity. Nano Research, 2018, 11(2): 905–912

[86] Hu M, Zhao S, Liu S, Chen C, Chen W, Zhu W, Liang C, Cheong W C, Wang Y, Yu Y, . MOF-confined sub-2 nm atomically ordered intermetallic PdZn nanoparticles as high-performance catalysts for selective hydrogenation of acetylene. Advanced Materials, 2018, 30(33): 1801878–1801884

[87] Hu M, Yang W, Liu S, Zhu W, Li Y, Hu B, Chen Z, Shen R, Cheong W C, Wang Y, . Topological self-template directed synthesis of multi-shelled intermetallic Ni₃Ga hollow microspheres for the selective hydrogenation of alkyne. Chemical Science (Cambridge), 2019, 10(2): 614–619

[88] Primo A, Neatu F, Florea M, Parvulescu V, Garcia H. Graphenes in the absence of metals as carbocatalysts for selective acetylene hydrogenation and alkene hydrogenation. Nature Communications, 2014, 5(1): 1–9

[89] Yang J, Zhang F, Lu H, Hong X, Jiang H, Wu Y, Li Y. Hollow Zn/Co ZIF particles derived from core-shell ZIF-67@ZIF-8 as selective catalyst for the semi-hydrogenation of acetylene. Angewandte Chemie International Edition, 2015, 54(37): 10889–10893

[90] Guilin Z, Puguang W, Jiang Z, Pinliang Y, Can L. Selective hydrogenation of acetylene over a MoP catalyst. Chinese Journal of Catalysis, 2011, 32(1–2): 27–30

[91] Borodziński A. The effect of palladium particle size on the kinetics of hydrogenation of acetylene-ethylene mixtures over Pd/SiO₂ catalysts. Catalysis Letters, 2001, 71(3–4): 169–175

[92] Asplund S. Coke formation and its effect on internal mass transfer and selectivity in Pd-catalysed acetylene hydrogenation. Journal of Catalysis, 1996, 158(1): 267–278

[93] Kim S K, Kim C, Lee J H, Kim J, Lee H, Moon S H. Performance of shape-controlled Pd nanoparticles in the selective hydrogenation of acetylene. Journal of Catalysis, 2013, 306: 146–154

[94] Leviness S, Nair V, Weiss A H, Schay Z, Guczi L. Acetylene hydrogenation selectivity control on PdCu/Al₂O₃ catalysts. Journal of Molecular Catalysis, 1984, 25(1–3): 131–140

[95] McGown W T, Kemball C, Whan D A, Scurrell M S. Hydrogenation of acetylene in excess ethylene on an alumina supported palladium catalyst in a static system. Journal of the Chemical Society, Faraday Transactions 1. Physical Chemistry in Condensed Phases, 1977, 73: 632–647

[96] Osswald J, Kovnir K, Armbrüster M, Giedigkeit R, Jentoft R E, Wild U, Grin Y, Schlögl R. Palladium-gallium intermetallic compounds for the selective hydrogenation of acetylene: Part II: Surface characterization and catalytic performance. Journal of Catalysis, 2008, 258(1): 219–227

[97] Panpranot J, Kontapakdee K, Praserthdam P. Effect of TiO₂ crystalline phase composition on the physicochemical and catalytic properties of Pd/TiO₂ in selective acetylene hydrogenation. Journal of Physical Chemistry B, 2006, 110(15): 8019–8024

[98] Pei G X, Liu X Y, Wang A, Li L, Huang Y, Zhang T, Lee J W, Jang B W, Mou C Y. Promotional effect of Pd single atoms on Au nanoparticles supported on silica for the selective hydrogenation of acetylene in excess ethylene. New Journal of Chemistry, 2014, 38(5): 2043–2051

[99] Pei G X, Liu X Y, Wang A, Lee A F, Isaacs M A, Li L, Pan X, Yang X, Wang X, Tai Z, . Ag alloyed Pd single-atom catalysts for efficient selective hydrogenation of acetylene to ethylene in excess ethylene. ACS Catalysis, 2015, 5(6): 3717–3725

[100] Ryndin Y A, Stenin M, Boronin A, Bukhtiyarov V, Zaikovskii V. Effect of Pd/C dispersion on its catalytic properties in acetylene and vinylacetylene hydrogenation. Applied Catalysis, 1989, 54(1): 277–288

[101] Tracey S, Palermo A, Vazquez J P H, Lambert R M. In situ electrochemical promotion by sodium of the selective hydrogenation of acetylene over platinum. Journal of Catalysis, 1998, 179(1): 231–240

[102] Xu Y, Jiang Y, Xu H, Wang Q, Huang W, He H, Zhai Y, Di S, Guo L, Xu X, . Highly selectivity catalytic hydrogenation of acetylene on Al₂O₃ supported palladium-imidazolium based ionic liquid phase. Applied Catalysis A, General, 2018, 567: 12–19

[103] Zhang Q, Li J, Liu X, Zhu Q. Synergetic effect of Pd and Ag dispersed on Al₂O₃ in the selective hydrogenation of acetylene. Applied Catalysis A, General, 2000, 197(2): 221–228

[104] Bond G C. Supported metal catalysts: some unsolved problems. Chemical Society Reviews, 1991, 20(4): 441–475

[105] Bugaev A L, Guda A A, Lazzarini A, Lomachenko K A, Groppo E, Pellegrini R, Piovano A, Emerich H, Soldatov A V, Bugaev L A, . In situ formation of hydrides and carbides in palladium catalyst: when XANES is better than EXAFS and XRD. Catalysis Today, 2017, 283: 119–126

[106] Vilé G, Pérez-Ramírez J. Beyond the use of modifiers in selective alkyne hydrogenation: silver and gold nanocatalysts in flow mode for sustainable alkene production. Nanoscale, 2014, 6(22): 13476–13482

[107] Luo Y, Alarcón Villaseca S, Friedrich M, Teschner D, Knop-Gericke A, Armbrüster M. Addressing electronic effects in the semi-hydrogenation of ethyne by InPd₂ and intermetallic Ga-Pd compounds. Journal of Catalysis, 2016, 338: 265–272

[108] Vignola E, Steinmann S N, Le Mapihan K, Vandegehuchte B D, Curulla D, Sautet P. Acetylene adsorption on Pd-Ag alloys: evidence for limited island formation and strong reverse segregation from Monte Carlo simulations. Journal of Physical Chemistry C, 2018, 122(27): 15456–15463

[109] Feng Q, Zhao S, Wang Y, Dong J, Chen W, He D, Wang D, Yang J, Zhu Y, Zhu H, . Isolated single-atom Pd sites in intermetallic nanostructures: high catalytic selectivity for semihydrogenation of alkynes. Journal of the American Chemical Society, 2017, 139(21): 7294–7301

[110] Menezes W, Altmann L, Zielasek V, Thiel K, Bäumer M. Bimetallic Co-Pd catalysts: study of preparation methods and their influence on the selective hydrogenation of acetylene. Journal of Catalysis, 2013, 300: 125–135

[111] Khan N A, Shaikhutdinov S, Freund H J. Acetylene and ethylene hydrogenation on alumina supported Pd-Ag model catalysts. Catalysis Letters, 2006, 108(3–4): 159–164

[112] López N, Vargas-Fuentes C. Promoters in the hydrogenation of alkynes in mixtures: insights from density functional theory. Chemical Communications, 2012, 48(10): 1379–1391

[113] Krajčí M, Hafner J. Selective semi-hydrogenation of acetylene: atomistic scenario for reactions on the polar threefold surfaces of GaPd. Journal of Catalysis, 2014, 312: 232–248

[114] Bridier B, Hevia M A, López N, Pérez-Ramírez J. Permanent alkene selectivity enhancement in copper-catalyzed propyne hydrogenation by temporary CO supply. Journal of Catalysis, 2011, 278(1): 167–172

[115] Cherkasov N, Ibhadon A O, McCue A J, Anderson J A, Johnston S K. Palladium-bismuth intermetallic and surface-poisoned catalysts for the semi-hydrogenation of 2-methyl-3-butyn-2-ol. Applied Catalysis A, General, 2015, 497: 22–30

[116] Kruppe C M, Krooswyk J D, Trenary M. Selective hydrogenation of acetylene to ethylene in the presence of a carbonaceous surface layer on a Pd/Cu (111) single-atom alloy. ACS Catalysis, 2017, 7(12): 8042–8049

[117] Miegge P, Rousset J, Tardy B, Massardier J, Bertolini J. Pd₁Ni₉₉ and Pd₅Ni₉₅: Pd surface segregation and reactivity for the hydrogenation of 1,3-butadiene. Journal of Catalysis, 1994, 149(2): 404–413

[118] Long Y, Li J, Wu L, Wang Q, Liu Y, Wang X, Song S, Zhang H. Construction of trace silver modified core@shell structured Pt-Ni nanoframe@CeO₂ for semihydrogenation of phenylacetylene. Nano Research, 2019, 12(4): 869–875

[119] Choe K, Zheng F, Wang H, Yuan Y, Zhao W, Xue G, Qiu X, Ri M, Shi X, Wang Y, . Fast and selective semihydrogenation of alkynes by palladium nanoparticles sandwiched in metal-organic frameworks. Angewandte Chemie, 2020, 132(9): 3679–3686

[120] Lorenz H, Zhao Q, Turner S, Lebedev O I, Van Tendeloo G, Klötzer B, Rameshan C, Pfaller K, Konzett J, Penner S. Origin of different deactivation of Pd/SnO₂ and Pd/GeO₂ catalysts in methanol dehydrogenation and reforming: a comparative study. Applied Catalysis A, General, 2010, 381(1–2): 242–252

[121] Cao Y, Zhang H, Ji S, Sui Z, Jiang Z, Wang D, Zaera F, Zhou X, Duan X, Li Y. Adsorption site regulation to guide atomic design of Ni-Ga catalysts for acetylene semi-hydrogenation. Angewandte Chemie, 2020, 132(28): 11744–11749

[122] Albani D, Shahrokhi M, Chen Z, Mitchell S, Hauert R, López N, Pérez-Ramírez J. Selective ensembles in supported palladium sulfide nanoparticles for alkyne semi-hydrogenation. Nature Communications, 2018, 9(1): 1–11

[123] Liang Y, Liu Q, Asiri A M, Sun X, Luo Y. Self-supported FeP nanorod arrays: a cost-effective 3D hydrogen evolution cathode with high catalytic activity. ACS Catalysis, 2014, 4(11): 4065–4069

[124] Xing Z, Liu Q, Asiri A M, Sun X. High-efficiency electrochemical hydrogen evolution catalyzed by tungsten phosphide submicroparticles. ACS Catalysis, 2014, 5(1): 145–149

[125] Shao L, Zhang W, Armbrüster M, Teschner D, Girgsdies F, Zhang B, Timpe O, Friedrich M, Schlögl R, Su D S. Nanosizing intermetallic compounds onto carbon nanotubes: active and selective hydrogenation catalysts. Angewandte Chemie International Edition, 2011, 50(43): 10231–10235

[126] Fang P, Tang Z J, Huang J H, Cen C P, Tang Z X, Chen X B. Using sewage sludge as a denitration agent and secondary fuel in a cement plant: a case study. Fuel Processing Technology, 2015, 137: 1–7

[127] Bauer M, Schoch R, Shao L, Zhang B, Knop-Gericke A, Willinger M, Schlögl R, Teschner D. Structure-activity studies on highly active palladium hydrogenation catalysts by X-ray absorption spectroscopy. Journal of Physical Chemistry C, 2012, 116(42): 22375–22385

[128] Bruix A, Rodriguez J A, Ramírez P J, Senanayake S D, Evans J, Park J B, Stacchiola D, Liu P, Hrbek J, Illas F. A new type of strong metal-support interaction and the production of H₂ through the transformation of water on Pt/CeO₂ (111) and Pt/CeO_x/TiO₂ (110) catalysts. Journal of the American Chemical Society, 2012, 134(21): 8968–8974

[129] Zhao J, Chen H, Xu J, Shen J. Effect of surface acidic and basic properties of the supported nickel catalysts on the hydrogenation of pyridine to piperidine. Journal of Physical Chemistry C, 2013, 117(20): 10573–10580

[130] Hoxha F, Schimmoeller B, Cakl Z, Urakawa A, Mallat T, Pratsinis S E, Baiker A. Influence of support acid-base properties on the platinum-catalyzed enantioselective hydrogenation of activated ketones. Journal of Catalysis, 2010, 271(1): 115–124

[131] Burton P D, Boyle T J, Datye A K. Facile, surfactant-free synthesis of Pd nanoparticles for heterogeneous catalysts. Journal of Catalysis, 2011, 280(2): 145–149

[132] Teschner D, Borsodi J, Kis Z, Szentmiklósi L, Révay Z, Knop-Gericke A, Schlögl R, Torres D, Sautet P. Role of hydrogen species in palladium-catalyzed alkyne hydrogenation. Journal of Physical Chemistry C, 2010, 114(5): 2293–2299

[133] Sa J, Arteaga G D, Daley R A, Bernardi J, Anderson J A. Factors influencing hydride formation in a Pd/TiO₂ catalyst. Journal of Physical Chemistry B, 2006, 110(34): 17090–17095

[134] Wilde M, Fukutani K, Ludwig W, Brandt B, Fischer J H, Schauermann S, Freund H J. Influence of carbon deposition on the hydrogen distribution in Pd nanoparticles and their reactivity in olefin hydrogenation. Angewandte Chemie International Edition, 2008, 47(48): 9289–9293

[135] Ludwig W, Savara A, Dostert K H, Schauermann S. Olefin hydrogenation on Pd model supported catalysts: new mechanistic insights. Journal of Catalysis, 2011, 284(2): 148–156

[136] Ludwig W, Savara A, Madix R J, Schauermann S, Freund H J. Subsurface hydrogen diffusion into Pd nanoparticles: role of low-coordinated surface sites and facilitation by carbon. Journal of Physical Chemistry C, 2012, 116(5): 3539–3544

[137] Tew M W, Nachtegaal M, Janousch M, Huthwelker T, van Bokhoven J A. The irreversible formation of palladium carbide during hydrogenation of 1-pentyne over silica-supported palladium nanoparticles: in situ Pd K and L 3 edge XAS. Physical Chemistry Chemical Physics, 2012, 14(16): 5761–5768

[138] Vogel W, He W, Huang Q H, Zou Z, Zhang X G, Yang H. Palladium nanoparticles “breathe” hydrogen: a surgical view with X-ray diffraction. International Journal of Hydrogen Energy, 2010, 35(16): 8609–8620

[139] Soldatov A, Della Longa S, Bianconi A. Relevant role of hydrogen atoms in the XANES of Pd hydride: evidence of hydrogen induced unoccupied states. Solid State Communications, 1993, 85(10): 863–868

[140] D’Angelo P, Benfatto M, Della Longa S, Pavel N. Combined XANES and EXAFS analysis of Co²⁺, Ni²⁺, and Zn²⁺ aqueous solutions. Physical Review. B, 2002, 66(6): 064209–064216

[141] Balde C P, Mijovilovich A E, Koningsberger D C, van der Eerden A M, Smith A D, de Jong K P, Bitter J H. XAFS study of the Al K-edge in NaAlH₄. Journal of Physical Chemistry C, 2007, 111(31): 11721–11725

[142] Mino L, Agostini G, Borfecchia E, Gianolio D, Piovano A, Gallo E, Lamberti C. Low-dimensional systems investigated by X-ray absorption spectroscopy: a selection of 2D, 1D and 0D cases. Journal of Physics. D, Applied Physics, 2013, 46(42): 423001–423074

[143] Bordiga S, Groppo E, Agostini G, van Bokhoven J A, Lamberti C. Reactivity of surface species in heterogeneous catalysts probed by in situ X-ray absorption techniques. Chemical Reviews, 2013, 113(3): 1736–1850

[144] van Bokhoven J A, Lamberti C. Structure of aluminum, iron, and other heteroatoms in zeolites by X-ray absorption spectroscopy. Coordination Chemistry Reviews, 2014, 277: 275–290

[145] Guda S A, Guda A A, Soldatov M A, Lomachenko K A, Bugaev A L, Lamberti C, Gawelda W, Bressler C, Smolentsev G, Soldatov A V, . Optimized finite difference method for the full-potential XANES simulations: application to molecular adsorption geometries in MOFs and metal-ligand intersystem crossing transients. Journal of Chemical Theory and Computation, 2015, 11(9): 4512–4521

[146] Langhammer C, Zhdanov V P, Zorić I, Kasemo B. Size-dependent hysteresis in the formation and decomposition of hydride in metal nanoparticles. Chemical Physics Letters, 2010, 488(1–3): 62–66

[147] Bugaev A L, Guda A A, Lomachenko K A, Srabionyan V V, Bugaev L A, Soldatov A V, Lamberti C, Dmitriev V P, van Bokhoven J A. Temperature- and pressure-dependent hydrogen concentration in supported PdH_x nanoparticles by Pd K-edge X-ray absorption spectroscopy. Journal of Physical Chemistry C, 2014, 118(19): 10416–10423

[148] Bugaev A L, Srabionyan V V, Soldatov A V, Bugaev L A, van Bokhoven J A. The role of hydrogen in formation of Pd XANES in Pd-nanoparticles. Journal of Physics: Conference Series, 2013, 430: 012028

[149] Yamauchi M, Ikeda R, Kitagawa H, Takata M. Nanosize effects on hydrogen storage in palladium. Journal of Physical Chemistry C, 2008, 112(9): 3294–3299

[150] Shabaev A, Papaconstantopoulos D, Mehl M, Bernstein N. First-principles calculations and tight-binding molecular dynamics simulations of the palladium-hydrogen system. Physical Review. B, 2010, 81(18): 184103–184112

[151] Shegai T, Langhammer C. Hydride formation in single palladium and magnesium nanoparticles studied by nanoplasmonic dark-field scatteringspectroscopy. Advanced Materials, 2011, 23(38): 4409–4414

[152] Teschner D, Borsodi J, Wootsch A, Révay Z, Hävecker M, Knop-Gericke A, Jackson S D, Schlögl R. The roles of subsurface carbon and hydrogen in palladium-catalyzed alkyne hydrogenation. Science, 2008, 320(5872): 86–89

[153] Stacchiola D, Molero H, Tysoe W. Palladium-catalyzed cyclotrimerization and hydrogenation: from ultrahigh vacuum to high-pressure catalysis. Catalysis Today, 2001, 65(1): 3–11

[154] García-Mota M, Bridier B, Pérez-Ramírez J, López N. Interplay between carbon monoxide, hydrides, and carbides in selective alkyne hydrogenation on palladium. Journal of Catalysis, 2010, 273(2): 92–102

[155] Narehood D, Kishore S, Goto H, Adair J H, Nelson J, Gutierrez H, Eklund P. X-ray diffraction and H-storage in ultra-small palladium particles. International Journal of Hydrogen Energy, 2009, 34(2): 952–960

[156] Borodziński A, Janko A. Flow reactor for kinetic studies with simultaneous X-ray phase analysis of a catalyst. Reaction Kinetics and Catalysis Letters, 1977, 7(2): 163–169

[157] Frackiewicz A. Hydrogenation of ethylene on thin films of palladium and palladium hydride. 1977

[158] Teschner D, Vass E, Hävecker M, Zafeiratos S, Schnörch P, Sauer H, Knop-Gericke A, Schlögl R, Chamam M, Wootsch A. Alkyne hydrogenation over Pd catalysts: a new paradigm. Journal of Catalysis, 2006, 242(1): 26–37

[159] Albers P, Pietsch J, Parker S F. Poisoning and deactivation of palladium catalysts. Journal of Molecular Catalysis A Chemical, 2001, 173(1–2): 275–286

[160] Pachulski A, Schödel R, Claus P. Performance and regeneration studies of Pd-Ag/Al₂O₃ catalysts for the selective hydrogenation of acetylene. Applied Catalysis A, General, 2011, 400(1–2): 14–24

[161] Liu R J, Crozier P, Smith C, Hucul D, Blackson J, Salaita G. Metal sintering mechanisms and regeneration of palladium/alumina hydrogenation catalysts. Applied Catalysis A, General, 2005, 282(1–2): 111–121

[162] Ahn I Y, Lee J H, Kum S S, Moon S H. Formation of C₄ species in the deactivation of a Pd/SiO₂ catalyst during the selective hydrogenation of acetylene. Catalysis Today, 2007, 123(1–4): 151–157

[163] Bolarinwa Ayodele O, Vinati S, Barborini E, Boddapati L, El Hajraoui K, Kröhnert J, Deepak F L, Trunschke A, Kolen’ko Y V. Selectivity boost in partial hydrogenation of acetylene via atomic dispersion of platinum over ceria. Catalysis Science & Technology, 2020, 10(22): 7471–7475

RIGHTS & PERMISSIONS

Higher Education Press