화학공학소재연구정보센터
Journal of Industrial and Engineering Chemistry, Vol.103, 67-79, November, 2021
Turning CO2 into di-methyl ether (DME) using Pd based catalysts - Role of Ca in tuning the activity and selectivity
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Herein, we report high-performance Pd and Ca-promoted Pd nanoparticles (NPs) (~2-6 nm) over mesoporous CeO2 with dual functionality of converting CO2 to methanol and its dehydration to di-methyl ether (DME) in a single catalyst bed prepared by a single-pot sol-gel chelating (SGC) method. Moreover, Ca promotion (0.5wt. %, optimized value) greatly improved the catalytic performance (XCO2: 30.5 %, SDME: 70.5 % and space time yield (STYDME): 5276 mmol/kgcat.hr at 325 °C and 20 Bar) by increasing Pd0 content over CeO2 and tuned the redox properties of CeO2 as well as basicity/acidity of tested samples as evidenced by the characterization results. In situ diffuse reflectance infrared fourier transform spectroscopy (DRIFTS) provided insights of the formation of DME and CH4 with visible respective IR bands along with the identification of various transient surface species emerged over the catalyst surface at actual reaction conditions which led us to propose a reaction mechanism following a formate route to methanol and its subsequent dehydration to dimethyl ether.
  1. Roy S, Cherevotan A, Peter SC, ACS Energy Lett., 3, 1938 (2018)
  2. Saravanan K, Ham H, Tsubaki N, Bae JW, Appl. Catal. B: Environ., 217, 494 (2017)
  3. Li Z, Wang J, Qu Y, Liu H, Tang C, Miao S, Feng Z, An H, Li C, ACS Catal., 7, 8544 (2017)
  4. Chen JY, Wang X, Wu DK, Zhang JL, Ma QX, Gao XH, Lai XY, Xia HQ, Fan SB, Zhao TS, Fuel, 239, 44 (2019)
  5. Zhang J, Su X, Wang X, Ma Q, Fan S, Zhao TS, React. Kinet. Mech. Catal., 124, 575 (2018)
  6. Wei J, Ge Q, Yao R, Wen Z, Fang C, Guo L, Xu H, Sun J, Nat. Commun., 8, 15174 (2017)
  7. Li Z, Qu Y, Wang J, Lin H, Li M, Miao S, Li C, Joule, 3, 570 (2019)
  8. Yang C, Mu R, Wang G, Song J, Tian H, Zhao ZJ, Gong J, Chem. Sci., 10, 3161 (2019)
  9. Alvarez A, Bansode A, Urakawa A, Bavykina AV, Wezendonk TA, Makkee M, Gascon J, Kapteijn F, Chem. Rev., 117(14), 9804 (2017)
  10. Sun J, Yang G, Yoneyama Y, Tsubaki N, ACS Catal., 4, 3346 (2014)
  11. Bonura G, Cannilla C, Frusteri L, Mezzapica A, Frusteri F, Catal. Today, 281, 337 (2017)
  12. Bonura G, Cannilla C, Frusteri L, Mezzapica A, Frusteri F, Catal. Today, 281, 337 (2017)
  13. Wender I, Fuel Process. Technol., 48(3), 189 (1996)
  14. Asthana S, Samanta C, Bhaumik A, Banerjee B, Voolapalli RK, Saha B, J. Catal., 334, 89 (2016)
  15. Huang MH, et al., international journal of hydrogen energy, 40, 13583 (2015).
  16. Aguayo AT, Erena J, Mier D, Arandes JM, Olazar M, Bilbao J, Ind. Eng. Chem. Res., 46(17), 5522 (2007)
  17. Ge QJ, Huang YM, Qiu FY, Li SB, Appl. Catal. A: Gen., 167(1), 23 (1998)
  18. Frusteri F, Migliori M, Cannilla C, Frusteri L, Catizzone E, Aloise A, Giordano G, Bonura G, J. CO2 Util., 18, 353 (2017)
  19. Allahyari S, Haghighi M, Ebadi A, Hosseinzadeh S, Energy Conv. Manag., 83, 212 (2014)
  20. Bonura G, Frusteri F, Cannilla C, Ferrante GD, Aloise A, Catizzone E, Migliori M, Giordano G, Catal. Today, 277, 48 (2016)
  21. Bansode A, Urakawa A, J. Catal., 309, 66 (2014)
  22. Bae JW, Kang SH, Lee YJ, Jun KW, J. Ind. Eng. Chem., 15(4), 566 (2009)
  23. Yang GH, Thongkam M, Vitidsant T, Yoneyama Y, Tan YS, Tsubaki N, Catal. Today, 171(1), 229 (2011)
  24. Garcia-Trenco A, Vidal-Moya A, Martinez A, Catal. Today, 179(1), 43 (2012)
  25. Stiefel M, Ahmad R, Arnold U, Doring M, Fuel Process. Technol., 92(8), 1466 (2011)
  26. Chen HJ, Fan CW, Yu CS, Appl. Energy, 101, 449 (2013)
  27. Moradi GR, Yaripour F, Vale-Sheyda P, Fuel Process. Technol., 91(5), 461 (2010)
  28. Phan XK, Walmsley JC, Bakhtiary-Davijany H, Myrstad R, Pfeifer P, Venvik H, Holmen A, Catal. Today, 273, 25 (2016)
  29. Shen WJ, Kobayashi A, Ichihashi Y, Matsumura Y, Haruta M, Catal. Lett., 73(2-4), 161 (2001)
  30. Luo MF, Hou ZY, Yuan XX, Zheng XM, Catal. Lett., 50(3-4), 205 (1998)
  31. Senanayake SD, Zhou J, Baddorf AP, Mullins DR, Surf. Sci., 601, 3215 (2007)
  32. Roy S, Hegde M, Catal. Commun., 9, 811 (2008)
  33. Craciun R, Daniell W, Knozinger H, Appl. Catal. A: Gen., 230(1-2), 153 (2002)
  34. Usami Y, Kagawa K, Kawazoe M, Matsumura Y, Sakurai H, Haruta M, Appl. Catal. A: Gen., 171(1), 123 (1998)
  35. Malik AS, Zaman SF, Al-Zahrani AA, Daous MA, Driss H, Petrov LA, Appl. Catal. A: Gen. (2018).
  36. Ojelade OA, Zaman SF, Daous MA, Al-Zahrani AA, Malik AS, Driss H, Shterk G, Gascon J, Appl. Catal. A: Gen., 584 (2019)
  37. Montini T, Melchionna M, Monai M, Fornasiero P, Chem. Rev., 116(10), 5987 (2016)
  38. Zhang Y, Bals S, Van Tendeloo G, Part. Part. Syst. Charact., 36, 180028 (2019)
  39. Rajkumar T, Sapi A, Abel M, Kiss J, Szenti I, Baan K, Gomez-Perez JF, Kukovecz A, Konya Z, Catal. Lett., 1 (2021).
  40. Bunluesin T, Gorte RJ, Graham GW, Appl. Catal. B: Environ., 15(1-2), 107 (1998)
  41. Hu Z, Liu X, Meng D, Guo Y, Guo Y, Lu G, ACS Catal., 6, 2265 (2016)
  42. Peng RS, Li SJ, Sun XB, Ren QM, Chen LM, Fu ML, Wu JL, Ye DQ, Appl. Catal. B: Environ., 220, 462 (2018)
  43. Trovarelli A, Catal. Rev.-Sci. Eng., 38(4), 439 (1996)
  44. Trujillo-Reyes J, Vilchis-Nestor AR, Majumdar S, Peralta-Videa JR, Gardea-Torresdey JL, J. Hazard. Mater., 263, 677 (2013)
  45. Masui T, Hirai H, Imanaka N, Adachi G, Sakata T, Mori H, J. Mater. Sci. Lett., 21(6), 489 (2002)
  46. Fan L, Zhang J, Ma K, Zhang Y, Hu YM, Kong L, Jia AP, Zhang Z, Huang W, Lu JQ, J. Catal., 397, 116 (2021)
  47. Cao F, Song Z, Zhang Z, Xiao YS, Zhang M, Hu X, Liu ZW, Qu Y, ACS Appl. Mater. Interfaces (2021).
  48. Haeussler A, Abanades S, Jouannaux J, Drobek M, Ayral A, Julbe A, AIMS Materials Science, 6, 657 (2019)
  49. Ramesh S, Upender G, Raju KJ, Padmaja G, Reddy SM, Reddy C, Effect of Ca on the properties of Gd-doped ceria for IT-SOFC, (2013).
  50. Song YQ, Liu XR, Xiao LF, Wu W, Zhang JW, Song XM, Catal. Lett., 145(6), 1272 (2015)
  51. Malik A, Zaman S, Al-Zahrani A, Daous M, Driss H, Petrov L, Bul. Chem. Commun., 189 (2018)
  52. Podila S, Zaman SF, Driss H, Al-Zahrani AA, Daous MA, Petrov LA, Int. J. Hydrog. Energy, 42(12), 8006 (2017)
  53. Sing KS, Williams RT, Adsorpt. Sci. Technol., 22, 773 (2004)
  54. De Lange MF, Vlugt TJ, Gascon J, Kapteijn F, Microporous Mesoporous Mater., 200, 199 (2014)
  55. Zhang ZH, Zhang LY, Yao SY, Song XZ, Huang WX, Hulsey MJ, Yan N, J. Catal., 376, 57 (2019)
  56. Sun Q, Chen BW, Wang N, He Q, Chang A, YAng CM, Asakura H, Tanaka T, Hulsey MJ, Wang CH, Angew. Chem.-Int. Edit., 132, 20358 (2020)
  57. Mierczynski P, Maniukiewicz W, Zaborowski M, Ciesielski R, Kedziora A, Maniecki TP, React. Kinet. Catal. Lett., 114, 211 (2015)
  58. Bernal S, Blanco G, El Amarti A, Cifredo G, Fitian L, Galtayries A, Martin J, Pintado J, Surf. Interface Analy., 38, 229 (2006)
  59. Fu Y, Hong T, Chen J, Auroux A, Shen J, Thermochim. Acta, 434, 22 (2005)
  60. Catizzone E, Aloise A, Migliori M, Giordano G, Appl. Catal. A: Gen., 502, 215 (2015)
  61. Gnanamani MK, Jacobs G, Shafer WD, Davis BH, ChemCatChem, 9, 492 (2017)
  62. Sasikala R, Gupta NM, Kulshreshtha SK, Catal. Lett., 71(1-2), 69 (2001)
  63. Lieske H, Volter J, J. Phys. Chem., 89 (1985)
  64. Wang LX, Xu SL, Chu WL, Yang WS, Catal. Today, 149(1-2), 163 (2010)
  65. Perez-Hernandez R, Avendano A, Rubio E, Rodriguez-Lugo V, Top. Catal., 54, 572 (2011)
  66. Wang CB, Lee HG, Yeh TF, Hsu SN, Chu KS, Thermochim. Acta, 401(2), 209 (2003)
  67. Hosseini M, Siffert S, Tidahy HL, Cousin R, Lamonier JF, Aboukais A, Vantomme A, Roussel M, Su BL, Catal. Today, 122(3-4), 391 (2007)
  68. Zhou RX, Zhao B, Yue BH, Appl. Surf. Sci., 254(15), 4701 (2008)
  69. INVALID CITATION
  70. Masek K, Beran J, Matolin V, Appl. Surf. Sci., 259, 34 (2012)
  71. Phung TK, Pham TLM, Nguyen ANT, Vu KB, Giang HN, Nguyen TA, Huynh TC, Pham HD, Chem. Eng. Technol., 43(4), 672 (2020)
  72. Liang XL, Dong X, Lin GD, Zhang HB, Appl. Catal. B: Environ., 88(3-4), 315 (2009)
  73. Peuckert M, J. Phys. Chem., 89, 2481 (1985)
  74. Beran J, Masek K, Vacuum, 167, 438 (2019)
  75. Yoo CJ, Lee DW, Kim MS, Moon DJ, Lee KY, J. Mol. Catal. A-Chem., 378, 255 (2013)
  76. Romeo M, Bak K, El Fallah J, Le Normand F, Hilaire L, Surf. Interface Anal., 20, 508 (1993)
  77. Choi EJ, Lee YH, Lee DW, Moon DJ, Lee KY, Mol. Catal., 434, 146 (2017)
  78. Beche E, Charvin P, Perarnau D, Abanades S, Flamant G, Surf. Interface Anal., 40, 264 (2008)
  79. Pfau A, Schierbaum K, Surf. Sci., 321, 71 (1994)
  80. Yang SC, Su WN, Rick J, Lin SD, Liu JY, Pan CJ, Lee JF, Hwang BJ, ChemSusChem, 6, 1326 (2013)
  81. Wenming C, Rui R, Duan W, Xiaodong W, Zhong J, Shitong H, J. Rare Earths, 35, 970 (2017)
  82. Esch F, Fabris S, Zhou L, Montini T, Africh C, Fornasiero P, Comelli G, Rosei R, Science, 309, 752 (2005)
  83. Li C, Sakata Y, Arai T, Domen K, Maruya KI, Onishi T, J. Chem. Soc.-Faraday Trans., 85, 929 (1989)
  84. Collins SE, Baltanas MA, Bonivardi AL, J. Catal., 226(2), 410 (2004)
  85. Schild C, Wokaun A, Baiker A, J. Mol. Catal., 63, 243 (1990)
  86. Wang YH, Gao WG, Wang H, Zheng YE, Na W, Li KZ, RSC Adv., 7, 8709 (2017)
  87. Cabilla GC, Bonivardi AL, Baltanas MA, J. Catal., 201(2), 213 (2001)
  88. Gibson DH, Coord. Chem. Rev., 185, 335 (1999)
  89. Burch R, Chalker S, Pritchard J, J. Chem. Soc.-Faraday Trans., 87, 193 (1991)
  90. Weigel J, Koeppel RA, Baiker A, Wokaun A, Langmuir, 12(22), 5319 (1996)
  91. Burcham LJ, Briand LE, Wachs IE, Langmuir, 17(20), 6164 (2001)
  92. Sheng Q, Ye RP, Gong W, Shi X, Xu B, Argyle M, Adidharma H, Fan M, J. Environ. Sci., 92, 106 (2020)
  93. Frusteri F, Cordaro M, Cannilla C, Bonura G, Appl. Catal. B: Environ., 162, 57 (2015)
  94. Ren J, Guo HL, Yang JZ, Qin ZF, Lin JY, Li Z, Appl. Surf. Sci., 351, 504 (2015)
  95. Lei H, Hou ZY, Xie JW, Fuel, 164, 191 (2016)
  96. Bahruji H, Bowker M, Hutchings G, Dimitratos N, Wells P, Gibson E, Jones W, Brookes C, Morgan D, Lalev G, J. Catal., 343, 133 (2016)
  97. Chang K, Zhang H, Cheng MJ, Lu Q, ACS Catal., 10, 613 (2019)
  98. Fan L, Fujimoto K, J. Catal., 150(1), 217 (1994)
  99. Ouyang B, Tan W, Liu B, Catal. Commun., 95, 36 (2017)
  100. Vayssilov GN, Lykhach Y, Migani A, Staudt T, Petrova GP, Tsud N, Skala T, Bruix A, Illas F, Prince KC, Matolin V, Neyman KM, Libuda J, Nat. Mater., 10(4), 310 (2011)
  101. Varga E, Pusztai P, Ovari L, Oszko A, Erdohelyi A, Papp C, Steinruck HP, Konya Z, Kiss J, PCCP, 17, 27154 (2015)
  102. Xu J, Long KZ, Wu F, Xue B, Li YX, Cao Y, Appl. Catal. A: Gen., 484, 1 (2014)
  103. Wamg S, Zhang L, Wang W, Zhao Y, Zhang G, Ma X, Gong J, Nanoscale, 5, 5582 (2013)
  104. Novak E, Fodor K, Szailer T, Oszko A, Erdohelyi A, Top. Catal., 20, 107 (2002)
  105. Li W, Wang H, Jiang X, Zhu J, Liu Z, Guo X, Song C, RSC Adv., 8, 7651 (2018)
  106. Liu RW, Qin ZZ, Ji HB, Su TM, Ind. Eng. Chem. Res., 52(47), 16648 (2013)
  107. Zhou XH, Su TM, Jiang YX, Qin ZZ, Ji HB, Guo ZH, Chem. Eng. Sci., 153, 10 (2016)
  108. Oyola-Rivera O, Baltanas MA, Cardona-Martinez N, J. CO2 Utiliz., 9, 8 (2015)
  109. Qin ZZ, Zhou XH, Su TM, Jiang YX, Ji HB, Catal. Commun., 75, 78 (2016)
  110. Li LY, Mao DS, Xiao J, Li L, Guo XM, Yu J, Chem. Eng. Res. Des., 111, 100 (2016)
  111. Naika SP, Ryu T, Bui V, Miller JD, Drinnan NB, Zmierczak W, Chem. Eng. J., 167(1), 362 (2011)
  112. Bonura G, Cordaro M, Spadaro L, Cannilla C, Arena F, Frusteri F, Appl. Catal. B: Environ., 140, 16 (2013)
  113. Qi GX, Fei JH, Zheng XM, Hou ZY, Catal. Lett., 72(1-2), 121 (2001)