Advanced TEM Characterization for Single-atom Catalysts: from Ex-situ Towards In-situ

Abstract

Clean energy innovation has triggered the development of single-atom catalysts(SACs) due to their excellent catalytic activity, high tunability and low cost. The success of SACs for many catalytic reactions has opened a new field where the fundamentals of catalytic property-structure relationship at atomic level await exploration, and thus raises challenges for structural characterization. Among the characterization techniques for SACs, aberration-corrected transmission electron microscopy(TEM) has become an essential tool for direct visualization of single atoms. In this review, we briefly summarize recent studies on SACs using advanced TEM. We first introduce TEM methods, which are particularly important for SACs characterization, and then discuss the applications of advanced TEM for SAC characterization, where not only atomic dispersion of single atoms can be studied, but also the distribution of elements and the valence state with local coordination can be resolved. We further extend our review towards in-situ TEM, which has increasing importance for the fundamental understanding of catalytic mechanism. Perspectives of TEM for SACs are finally discussed.

Keywords

Single-atom catalyst / Transmission electron microscopy (TEM) / Scanning transmission electron microscopy(STEM) / Electron energy loss spectroscopy(EELS) / Energy dispersive X-ray spectroscopy(EDX) / In-situ TEM

References

[1] Debe M K. Nature, 2012, 486: 43.

[2] Wu H B, Lou X W. Sci. Adv., 2017, 3: eaap9252.

[3] Zhang J, Sun B, Zhao Y, Kretschmer K, Wang G. Angew. Chem. Int. Ed., 2017, 56: 8505.

[4] Yang Y, Yang Y, Pei Z, Wu K-H, Tan C, Wang H, Wei L, Mahmood A, Yan C, Dong J, Zhao S, Chen Y. Matter, 2020, 3: 1442.

[5] Tian H, Tian H, Wang S, Chen S, Zhang F, Song L, Liu H, Liu J, Wang G. Nat. Commun., 2020, 11: 5025.

[6] Choi J, Suryanto B H R, Wang D, Du H L, Hodgetts R Y, Ferrero Vallana F M, MacFarlane D R, Simonov A N. Nat. Commun., 2020, 11: 5546.

[7] Zhang Y, Guo S-X, Zhang X, Bond A M, Zhang J. Nano Today, 2020, 31: 100835.

[8] Lacey S D, Dong Q, Huang Z, Luo J, Xie H, Lin Z, Kirsch D J, Vattipalli V, Povinelli C, Fan W, Shahbazian-Yassar R, Wang D, Hu L. Nano Lett., 2019, 19: 5149.

[9] Zhang L, Liu H, Liu S, Norouzi Banis M, Song Z, Li J, Yang L, Markiewicz M, Zhao Y, Li R, Zheng M, Ye S, Zhao Z-J, Botton G A, Sun X. ACS Catal., 2019, 9: 9350.

[10] Zhao C X, Li B Q, Liu J N, Zhang Q. Angew. Chem. Int. Ed., 2021, 60: 4448.

[11] Wang Y, Su H, He Y, Li L, Zhu S, Shen H, Xie P, Fu X, Zhou G, Feng C, Zhao D, Xiao F, Zhu X, Zeng Y, Shao M, Chen S, Wu G, Zeng J, Wang C. Chem. Rev., 2020, 120: 12217.

[12] Luo Z, Li J, Li Y, Wu D, Zhang L, Ren X, He C, Zhang Q, Gu M, Sun X. Adv. Energy Mater., 2022, 12: 2103823.

[13] Gao C, Low J, Long R, Kong T, Zhu J, Xiong Y. Chem. Rev., 2020, 120: 12175.

[14] Su L, Wang P, Wang J, Zhang D, Wang H, Li Y, Zhan S, Gong J. Adv. Funct. Mater., 2021, 31: 2104343.

[15] Wang K, Jiang L, Xin T, Li Y, Wu X, Zhang G. Chem. Eng. J., 2022, 42: 132229.

[16] Zhou P, Chen H, Chao Y, Zhang Q, Zhang W, Lv F, Gu L, Zhao Q, Wang N, Wang J, Guo S. Nat. Commun., 2021, 12: 4412.

[17] Xia Y, Sayed M, Zhang L, Cheng B, Yu J. Chem. Catal., 2021, 1: 1173.

[18] Xia B, Zhang Y, Ran J, Jaroniec M, Qiao S Z. ACS Cent. Sci., 2021, 7: 39.

[19] Li C, Li J, Huang Y, Liu J, Ma M, Liu K, Zhao C, Wang Z, Qu S, Zhang L, Han H, Deng W, Wang Z. J. Semicond., 2022, 43: 021701.

[20] Lian Z, Yang M, Jan F, Li B. J. Phys. Chem. Lett., 2021, 12: 7053.

[21] Cui T, Wang Y P, Ye T, Wu J, Chen Z, Li J, Lei Y, Wang D, Li Y. Angew. Chem. Int. Ed., 2022, 61: e202115219.

[22] Zhu H, Sha M, Zhao H, Nie Y, Sun X, Lei Y. J. Semicond., 2020, 41: 092701.

[23] Zhang Q, Guan J. Adv. Funct. Mater., 2020, 30: 2000768.

[24] Xie X, Peng L, Yang H, Waterhouse G I N, Shang L, Zhang T. Adv. Mater., 2021, 33: e2101038.

[25] Kaiser S K, Chen Z, Faust Akl D, Mitchell S, Perez-Ramirez J. Chem. Rev., 2020, 120: 11703.

[26] Chen C H, Wu D, Li Z, Zhang R, Kuai C G, Zhao X R, Dong C K, Qiao S Z, Liu H, Du X W. Adv. Energy Mater., 2019, 9: 1803913.

[27] Jiang K, Liu B, Luo M, Ning S, Peng M, Zhao Y, Lu Y R, Chan T S, de Groot F M F, Tan Y. Nat. Commun., 2019, 10: 1743.

[28] Wang J, Yang H, Li F, Li LG, Wu J B, Liu S H, Cheng T, Xu Y, Shao Q, Huang X Q. Sci. Adv., 2022, 8: eabl9271.

[29] Babu D D, Huang Y, Anandhababu G, Wang X, Si R, Wu M, Li Q, Wang Y, Yao J. J. Mater. Chem. A, 2019, 7: 8376.

[30] Yin J, Jin J, Lu M, Huang B, Zhang H, Peng Y, Xi P, Yan C H. J. Am. Chem. Soc., 2020, 142: 18378.

[31] Yang G, Zhu J, Yuan P, Hu Y, Qu G, Lu B A, Xue X, Yin H, Cheng W, Cheng J, Xu W, Li J, Hu J, Mu S, Zhang J N. Nat. Commun., 2021, 12: 1734.

[32] Kulkarni A, Siahrostami S, Patel A, Norskov J K. Chem. Rev., 2018, 118: 2302.

[33] Lin Z, Huang H, Cheng L, Hu W, Xu P, Yang Y, Li J, Gao F, Yang K, Liu S, Jiang P, Yan W, Chen S, Wang C, Tong H, Huang M, Zheng W, Wang H, Chen Q. Adv. Mater., 2021, 33: e2107103.

[34] Chen S, Luo T, Li X, Chen K, Fu J, Liu K, Cai C, Wang Q, Li H, Chen Y, Ma C, Zhu L, Lu Y R, Chan T S, Zhu M, Cortes E, Liu M. J. Am. Chem. Soc., 2022, 144: 14505.

[35] Teng Z, Zhang Q, Yang H, Kato K, Yang W, Lu Y-R, Liu S, Wang C, Yamakata A, Su C, Liu B, Ohno T. Nat. Catal., 2021, 4: 374.

[36] Zhang Q, Tan X, Bedford N M, Han Z, Thomsen L, Smith S, Amal R, Lu X. Nat. Commun., 2020, 11: 4181.

[37] Wang Z, Ke X, Zhou K, Xu X, Jin Y, Wang H, Sui M. J. Mater. Chem. A, 2021, 9: 18515.

[38] Wang M, Kong L, Lu X, Lawrence Wu C-M. J. Mater. Chem. A, 2022, 10: 9048.

[39] Ren W, Tan X, Yang W, Jia C, Xu S, Wang K, Smith S C, Zhao C. Angew.Chem.Int. Ed., 2019, 58: 6972.

[40] Zhao C, Dai X, Yao T, Chen W, Wang X, Wang J, Yang J, Wei S, Wu Y, Li Y. J. Am. Chem. Soc., 2017, 139: 8078.

[41] Li Y, Li J, Huang J, Chen J, Kong Y, Yang B, Li Z, Lei L, Chai G, Wen Z, Dai L, Hou Y. Angew. Chem. Int. Ed., 2021, 60: 9078.

[42] Xue Z, Zhang X, Qin J, Liu R. Nano Energy, 2021, 80: 105527.

[43] Geng J, Zhang S, Xu H, Wang G, Zhang H. Chem. Commun., 2021, 57: 5410.

[44] Chen Y, Wang P, Hao H, Hong J, Li H, Ji S, Li A, Gao R, Dong J, Han X, Liang M, Wang D, Li Y. J. Am. Chem. Soc., 2021, 143: 18643.

[45] Li Z, Chen Y, Ji S, Tang Y, Chen W, Li A, Zhao J, Xiong Y, Wu Y, Gong Y, Yao T, Liu W, Zheng L, Dong J, Wang Y, Zhuang Z, Xing W, He C T, Peng C, Cheong W C, Li Q, Zhang M, Chen Z, Fu N, Gao X, Zhu W, Wan J, Zhang J, Gu L, Wei S, Hu P, Luo J, Li J, Chen C, Peng Q, Duan X, Huang Y, Chen X M, Wang D, Li Y. Nat. Chem., 2020, 12: 764.

[46] Qi H, Yang J, Liu F, Zhang L, Yang J, Liu X, Li L, Su Y, Liu Y, Hao R, Wang A, Zhang T. Nat. Commun., 2021, 12: 3295.

[47] Tian S, Fu Q, Chen W, Feng Q, Chen Z, Zhang J, Cheong W C, Yu R, Gu L, Dong J, Luo J, Chen C, Peng Q, Draxl C, Wang D, Li Y. Nat. Commun., 2018, 9: 2353.

[48] Wang J, You R, Zhao C, Zhang W, Liu W, Fu X-P, Li Y, Zhou F, Zheng X, Xu Q, Yao T, Jia C-J, Wang Y-G, Huang W, Wu Y. ACS Catal., 2020, 10: 2754.

[49] Xiong Y, Dong J, Huang Z Q, Xin P, Chen W, Wang Y, Li Z, Jin Z, Xing W, Zhuang Z, Ye J, Wei X, Cao R, Gu L, Sun S, Zhuang L, Chen X, Yang H, Chen C, Peng Q, Chang C R, Wang D, Li Y. Nat. Nanotechnol., 2020, 15: 390.

[50] Qiao B, Wang A, Yang X, Allard L F, Jiang Z, Cui Y, Liu J, Li J, Zhang T. Nat. Chem., 2011, 3: 634.

[51] Han L, Cheng H, Liu W, Li H, Ou P, Lin R, Wang H T, Pao C W, Head A R, Wang C H, Tong X, Sun C J, Pong W F, Luo J, Zheng J C, Xin H L. Nat. Mater., 2022, 21: 681.

[52] He X, He Q, Deng Y, Peng M, Chen H, Zhang Y, Yao S, Zhang M, Xiao D, Ma D, Ge B, Ji H. Nat. Commun., 2019, 10: 3663.

[53] Liang S, Zhu C, Zhang N, Zhang S, Qiao B, Liu H, Liu X, Liu Z, Song X, Zhang H, Hao C, Shi Y. Adv. Mater., 2020, 32: e2000478.

[54] Liu X, Luo Y, Ling C, Shi Y, Zhan G, Li H, Gu H, Wei K, Guo F, Ai Z, Zhang L. Appl. Catal. B: Environ., 2022, 301: 120766.

[55] Peng X, Mi Y, Bao H, Liu Y, Qi D, Qiu Y, Zhuo L, Zhao S, Sun J, Tang X, Luo J, Liu X. Nano Energy, 2020, 78: 105321.

[56] Wang Q, Liu K, Fu J, Cai C, Li H, Long Y, Chen S, Liu B, Li H, Li W, Qiu X, Zhang N, Hu J, Pan H, Liu M. Angew. Chem. Int. Ed., 2021, 60: 25241.

[57] Yang Q, Peng H, Zhang Q, Qian X, Chen X, Tang X, Dai S, Zhao J, Jiang K, Yang Q, Sun J, Zhang L, Zhang N, Gao H, Lu Z, Chen L. Adv. Mater., 2021, 33: e2103186.

[58] Zheng T, Liu C, Guo C, Zhang M, Li X, Jiang Q, Xue W, Li H, Li A, Pao C W, Xiao J, Xia C, Zeng J. Nat. Nanotechnol., 2021, 16: 1386.

[59] Zhou P, Chao Y, Lv F, Wang K, Zhang W, Zhou J, Chen H, Wang L, Li Y, Zhang Q, Gu L, Guo S. ACS Catal., 2020, 10: 9109.

[60] Kasamatsu Y, Toyomura K, Haba H, Yokokita T, Shigekawa Y, Kino A, Yasuda Y, Komori Y, Kanaya J, Huang M, Murakami M, Kikunaga H, Watanabe E, Yoshimura T, Morita K, Mitsugashira T, Takamiya K, Ohtsuki T, Shinohara A. Nat. Chem., 2021, 13: 226.

[61] Wang S, Sun M, Zheng L, Zhou S. Chem Catal., 2021, 1: 1322.

[62] Zhang Y, Qi L, Lund A, Lu P, Bell A T. J. Am. Chem. Soc., 2021, 143: 8352.

[63] Asakura H N K, Ichikuni N, Iwasawa Y. Appl. Catal. A: Gen., 1999, 188: 313.

[64] Fu Q, Saltsburg H, Flytzani-Stephanopoulos M. Science, 2003, 301: 935.

[65] Hackett S F J, Brydson R M, Gass M H, Harvey I, Newman A D, Wilson K, Lee A F. Angew. Chem., 2007, 119: 8747.

[66] Kottwitz M, Li Y, Wang H, Frenkel A I, Nuzzo R G. Chemistry: Methods, 2021, 1: 278.

[67] Qi P, Wang J, Djitcheu X, He D, Liu H, Zhang Q. RSC Adv., 2022, 12: 1216.

[68] Egerton R F, Watanabe M. Ultramicroscopy, 2018, 193: 111.

[69] Tieu P, Yan X, Xu M, Christopher P, Pan X. Small, 2021, 17: e2006482.

[70] Gao Z., Li A., Ma D., Zhou W., Topics in Catalysis, 2022, https://doi.org/10.1007/s11244-022-01577-7

[71] Van Tendeloo G, Bals S, Van Aert S, Verbeeck J, Van Dyck D. Adv. Mater., 2012, 24: 5655.

[72] Howie A. Microscopy and Microanalysis, 2011, 17: 1022.

[73] Wang Q, Huang X, Zhao Z L, Wang M, Xiang B, Li J, Feng Z, Xu H, Gu M. J. Am. Chem. Soc., 2020, 142: 7425.

[74] Song B, Yang T T, Yuan Y, Sharifi-Asl S, Cheng M, Saidi W A, Liu Y, Shahbazian-Yassar R. ACS Nano, 2020, 14: 4074.

[75] Wu F, Yao N. Nano Energy, 2015, 13: 735.

[76] Williams D B, Carter C B. Transmission Electron Microscopy, 2009, New York: Springer.

[77] Egerton R F. Electron Energy: Loss Spectroscopy in the Electron Microscope, 2011, New York: Springer Science & Business Media.

[78] Senga R, Suenaga K. Nat. Commun., 2015, 6: 7943.

[79] Hu C, Dai L. Adv. Mater., 2019, 31: e1804672.

[80] Inagaki M, Toyoda M, Soneda Y, Morishita T. Carbon, 2018, 132: 104.

[81] Chen Y N, Zhang X, Zhou Z. Small Methods, 2019, 3: 1900050.

[82] Lu Z, Wang B, Hu Y, Liu W, Zhao Y, Yang R, Li Z, Luo J, Chi B, Jiang Z, Li M, Mu S, Liao S, Zhang J, Sun X. Angew. Chem. Int. Ed., 2019, 58: 2622.

[83] Yan H, Lin Y, Wu H, Zhang W, Sun Z, Cheng H, Liu W, Wang C, Li J, Huang X, Yao T, Yang J, Wei S, Lu J. Nat. Commun., 2017, 8: 1070.

[84] Li P, Wang M, Duan X, Zheng L, Cheng X, Zhang Y, Kuang Y, Li Y, Ma Q, Feng Z, Liu W, Sun X. Nat. Commun., 2019, 10: 1711.

[85] Zhang J, Liu J, Xi L, Yu Y, Chen N, Sun S, Wang W, Lange K M, Zhang B. J. Am. Chem. Soc., 2018, 140: 3876.

[86] Wang G, Zhang G, Ke X, Chen X, Chen X, Wang Y, Huang G, Dong J, Chu S, Sui M. Small, 2022, 18: e2107238.

[87] Li S, Liu J, Yin Z, Ren P, Lin L, Gong Y, Yang C, Zheng X, Cao R, Yao S, Deng Y, Liu X, Gu L, Zhou W, Zhu J, Wen X, Xu B, Ma D. ACS Catal., 2019, 10: 907.

[88] Cao X, Mirjalili A, Wheeler J, Xie W, Jang B W L. Front. Chem. Sci. Eng., 2015, 9: 442.

[89] Zhang T, Walsh A G, Yu J, Zhang P. Chem. Soc. Rev., 2021, 50: 569.

[90] Yao Y, Hu S, Chen W, Huang Z-Q, Wei W, Yao T, Liu R, Zang K, Wang X, Wu G, Yuan W, Yuan T, Zhu B, Liu W, Li Z, He D, Xue Z, Wang Y, Zheng X, Dong J, Chang C-R, Chen Y, Hong X, Luo J, Wei S, Li W-X, Strasser P, Wu Y, Li Y. Nat. Catal., 2019, 2: 304.

[91] Hannagan R T, Giannakakis G, Réocreux R, Schumann J, Finzel J, Wang Y C, Michaelides A, Deshlahra P, Christopher P, Flytzani-Stephanopoulos M, Stamatakis M, Sykes E C H. Science, 2021, 372: 1444.

[92] Peng Y, Geng Z, Zhao S, Wang L, Li H, Wang X, Zheng X, Zhu J, Li Z, Si R, Zeng J. Nano Lett., 2018, 18: 3785.

[93] Liu H, Jin P, Xue Y M, Dong C, Li X, Tang C C, Du X W. Angew. Chem. Int. Ed., 2015, 54: 7051.

[94] Xiao J, Liu P, Wang C X, Yang G W. Prog. Mater. Sci., 2017, 87: 140.

[95] Chinchilla L E, Olmos C M, Villa A, Carlsson A, Prati L, Chen X, Blanco G, Calvino J J, Hungría A B. Catal. Today, 2015, 253: 178.

[96] Maris E, Ketchie W, Murayama M, Davis R. J. Catal., 2007, 251: 281.

[97] Park J, Lee S, Kim H E, Cho A, Kim S, Ye Y, Han J W, Lee H, Jang J H, Lee J. Angew. Chem. Int. Ed., 2019, 58: 16038.

[98] Tao H, Choi C, Ding L-X, Jiang Z, Han Z, Jia M, Fan Q, Gao Y, Wang H, Robertson A W, Hong S, Jung Y, Liu S, Sun Z. Chem., 2019, 5: 204.

[99] Shi Z, Wang Y, Li J, Wang X, Wang Y, Li Y, Xu W, Jiang Z, Liu C, Xing W, Ge J. Joule, 2021, 5: 2164.

[100] Shan J, Ye C, Chen S, Sun T, Jiao Y, Liu L, Zhu C, Song L, Han Y, Jaroniec M, Zhu Y, Zheng Y, Qiao S Z. J. Am. Chem. Soc., 2021, 143: 5201.

[101] Qi K, Cui X, Gu L, Yu S, Fan X, Luo M, Xu S, Li N, Zheng L, Zhang Q, Ma J, Gong Y, Lv F, Wang K, Huang H, Zhang W, Guo S, Zheng W, Liu P. Nat. Commun., 2019, 10: 5231.

[102] Zhao X, Gao P, Yan Y, Li X, Xing Y, Li H, Peng Z, Yang J, Zeng J. J. Mater. Chem. A, 2017, 5: 20202.

[103] Guo X, Gao H, Wang S, Yang G, Zhang X, Zhang J, Liu H, Wang G. Nano Lett., 2022, 22: 1225.

[104] Zhang J, Wang E, Cui S, Yang S, Zou X, Gong Y. Nano Lett., 2022, 22: 1398.

[105] He B, Zhang Y, Liu X, Chen L. ChemCatChem, 2020, 12: 1853.

[106] Fang Z, Liu Y, Song C, Tao P, Shang W, Deng T, Zeng X, Wu J. J. Semicond., 2022, 43: 041104.

[107] Zhang L, Wang K, Deng Q, Li W, Zhang X, Liu X. DNA and Cell Biology, 2019, 38: 1346.

[108] Wu X, Ke X, Sui M. J. Semicond., 2022, 43: 041106.

[109] Wei S, Li A, Liu J C, Li Z, Chen W, Gong Y, Zhang Q, Cheong W C, Wang Y, Zheng L, Xiao H, Chen C, Wang D, Peng Q, Gu L, Han X, Li J, Li Y. Nat. Nanotechnol., 2018, 13: 856.

[110] Poerwoprajitno A R, Gloag L, Watt J, Cheong S, Tan X, Lei H, Tahini H A, Henson A, Subhash B, Bedford N M, Miller B K, O’Mara P B, Benedetti T M, Huber D L, Zhang W, Smith S C, Gooding J J, Schuhmann W, Tilley R D. Nat. Catal., 2022, 5: 231.

[111] DeRita L, Resasco J, Dai S, Boubnov A, Thang H V, Hoffman A S, Ro I, Graham G W, Bare S R, Pacchioni G, Pan X, Christopher P. Nat. Mater., 2019, 18: 746.

[112] Jiang S, Dai Q, Guo J, Li Y. J. Semicond., 2022, 43: 041101.

[113] Hulsey M J, Zhang B, Ma Z, Asakura H, Do D A, Chen W, Tanaka T, Zhang P, Wu Z, Yan N. Nat. Commun., 2019, 10: 1330.

[114] Lien H T, Chang S T, Chen P T, Wong D P, Chang Y C, Lu Y R, Dong C L, Wang C H, Chen K H, Chen L C. Nat. Commun., 2020, 11: 4233.

[115] Hoang S, Guo Y, Binder A J, Tang W, Wang S, Liu J J, Tran H, Lu X, Wang Y, Ding Y, Kyriakidou E A, Yang J, Toops T J, Pauly T R, Ramprasad R, Gao P X. Nat. Commun., 2020, 11: 1062.

[116] Shan J, Liu J, Li M, Lustig S, Lee S, Flytzani-Stephanopoulos M. Appl. Catal. B: Environ., 2018, 226: 534.

[117] Dreimann J M, Kohls E, Warmeling H F W, Stein M, Guo L F, Garland M, Dinh T N, Vorholt A J. ACS Catalysis, 2019, 9: 4308.

[118] Jiang Y, Chen Z, Han Y, Deb P, Gao H, Xie S, Purohit P, Tate M W, Park J, Gruner S M, Elser V, Muller D A. Nature, 2018, 559: 343.

[119] Ophus C. Microsc. Microanal., 2019, 25: 563.

[120] Ke X, Zhang M, Zhao K, Su D. Small Methods, 2022, 6: 2101040.

[121] Mitchell S, Pares F, Faust Akl D, Collins S M, Kepaptsoglou D M, Ramasse Q M, Garcia-Gasulla D, Perez-Ramirez J, Lopez N. J. Am. Chem. Soc., 2022, 144: 8018.

[122] Wang Z, Ke X, Sui M. Front. Chem., 2022, 10: 872117.