Synergy between single atoms and nanoclusters of Pd/g-C3N4 catalysts for efficient base-free CO2 hydro-genation to formic acid

doi:10.1016/S1872-2067(22)64202-5

Abstract

Abstract:

In base-free CO₂ hydrogenation to HCOOH over C₃N₄-supported Pd catalysts, a synergy between Pd single atoms and nanoclusters has been discovered by observing the highest catalytic activity when an optimum ratio of the two Pd states is present in the catalyst. It is demonstrated that Pd clusters are mainly involved in H₂ activation by dissociative adsorption, while single atoms are more effective for CO₂ activation. Thus, at an optimum single atom ratio (number of single atoms/number of single atoms + nanoclusters) of 41%, the catalyst shows the highest activity, which is superior to all Pd catalysts reported previously in the literature under the similar reaction conditions.

Key words: Base-free CO₂ hydrogenation to HCOOH, Pd/g-C₃N₄, Single atom catalyst, Nanocluster catalyst, Synergistic effect

Eun Hyup Kim, Min Hee Lee, Jeehye Kim, Eun Cheol Ra, Ju Hyeong Lee, Jae Sung Lee. Synergy between single atoms and nanoclusters of Pd/g-C₃N₄ catalysts for efficient base-free CO₂ hydro-genation to formic acid[J]. Chinese Journal of Catalysis, 2023, 47: 214-221.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64202-5

https://www.cjcatal.com/EN/Y2023/V47/I4/214

Figures/Tables 5

Fig. 1. (a) XRD patterns of Pd/g-C3N4 catalysts of various Pd loadings in comparison with reference patterns of C3N4 (black), Pd (gray) and PdO (green); HAADF-STEM images of 0.5 wt% Pd/CN (b), 1 wt% Pd/CN (c), 2 wt% Pd/CN (d), 3 wt% Pd/CN (e), and 4 wt% Pd/CN (f) samples. Insets show single atom ratios (yellow bar) and particle size distributions of nanoclusters with noted average sizes in each sample. X-axis: particle sizes. Y-axis: SA ratio (yellow) and frequency (red).

Table 1 Properties of Pd/CN catalysts.

Catalyst	BET ^a (m² g^‒1)	Pd ^b (wt%)	Size ^c (nm)	Dispersion ^d	SA ^e (%)	CO₂ desorbed^f(μmol m^‒2)
g-C₃N₄	138.51	—	—	—	—	0.0121
0.5 wt% Pd/CN	110.34	0.46	1.98	0.56	92	0.0140
1 wt% Pd/CN	102.03	0.89	2.54	0.44	67	0.0144
2 wt% Pd/CN	98.57	1.7	2.69	0.41	41	0.0146
3 wt% Pd/CN	71.16	3.46	3.11	0.36	26	0.01433
4 wt% Pd/CN	57.57	4.78	3.47	0.32	11	0.0142

Fig. 2. XANES (a) and EXAFS (b) of Pd K edges, and XPS Pd 3d spectra (c) of reduced Pd/CN catalysts compared with references of Pd foil and PdO.

Fig. 3. Activity of Pd/CN catalysts for base-free CO2 hydrogenation to HCOOH at 40 °C, 50 bar with a CO2/H2 ratio of 1:1 in distilled water presented in Pd-time yield (PTY) and HCOOH yield against Pd loading (wt%) (a), and turnover frequency (TOF) against single atom ratio (SA) (b).

Fig. 4. TPD of CO2 (a) and H2 (b). For TPD, 10 vol%CO2/He or H2/Ar flew through 50 mg of the catalyst at a temperature ramping rate of 10 °C min-1.

References

[1]	J. A. Patz, D. Campbell-Lendrum, T. Holloway, J. A. Foley, Nature, 2005, 438, 310-317.
[2]	Q. Schiermeier, Nature, 2011, 470, 316.
[3]	K. E. Trenberth, A. Dai, G. Van Der Schrier, P. D. Jones, J. Barichivich, K. R. Briffa, J. Sheffield, Nat. Clim. Change, 2014, 4, 17-22.
[4]	J. D. Shakun, P. U. Clark, F. He, S. A. Marcott, A. C. Mix, Z. Liu, B. Otto-Bliesner, A. Schmittner, E. Bard, Nature, 2012, 484, 49-54.
[5]	S. J. Davis, K. Caldeira, H. D. Matthews, Science, 2010, 329, 1330-1333.
[6]	R. S. Haszeldine, Science, 2009, 325, 1647-1652.
[7]	S. Saeidi, N. A. S. Amin, M. R. Rahimpour, J. CO₂ Util., 2014, 5, 66-81.
[8]	P. R. Yaashikaa, P. Senthil Kumar, S. J. Varjani, A. Saravanan, J. CO₂ Util., 2019, 33, 131-147.
[9]	A. Saravanan, P. Senthil kumar, D.-V. N. Vo, S. Jeevanantham, V. Bhuvaneswari, V. Anantha Narayanan, P. R. Yaashikaa, S. Swetha, B. Reshma, Chem. Eng. Sci., 2021, 236, 116515.
[10]	M. Rumayor, A. Dominguez-Ramos, A. Irabien, Appl. Sci., 2018, 8, 914.
[11]	J. Eppinger, K.-W. Huang, ACS Energy Lett., 2016, 2, 188-195.
[12]	C. Rice, S. Ha, R. I. Masel, P. Waszczuk, A. Wieckowski, T. Barnard, J. Power Sources, 2002, 111, 83-89.
[13]	I. Dutta, S. Chatterjee, H. Cheng, R. K. Parsapur, Z. Liu, Z. Li, E. Ye, H. Kawanami, J. S. C. Low, Z. Lai, X. J. Loh, K. W. Huang, Adv. Energy Mater., 2022, 12, 2103799.
[14]	J. Hietala, A. Vuori, P. Johnsson, I. Pollari, W. Reutemann, H. Kieczka, Formic Acid. in Ullmann’s Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, Germany, 2011, 1-22.
[15]	G. A. Filonenko, W. L. Vrijburg, E. J. M. Hensen, E. A. Pidko, J. Catal., 2016, 343, 97-105.
[16]	X. Lu, D. Y. C. Leung, H. Wang, M. K. H. Leung, J. Xuan, ChemElectroChem, 2014, 1, 836-849.
[17]	R. Cauwenbergh, S. Das, Green Chem., 2021, 23, 2553-2574.
[18]	F. M. Schwarz, J. Moon, F. Oswald, V. Müller, Joule, 2022, 6, 1304-1319.
[19]	D. Preti, C. Resta, S. Squarcialupi, G. Fachinetti, Angew. Chem. Int. Ed., 2011, 50, 12551-12554.
[20]	K. Rohmann, J. Kothe, M. W. Haenel, U. Englert, M. Hölscher, W. Leitner, Angew. Chem. Int. Ed., 2016, 55, 8966-8969.
[21]	W. Wang, Y. Himeda, Recent Advances in Transition Metal-Catalysed Homogeneous Hydrogenation of Carbon Dioxide in Aqueous Media, Karamé (ed.), Hydrogenation, IntechOpen, London. 2012, 10.5772/48658.
[22]	H. Park, J. H. Lee, E. H. Kim, K. Y. Kim, Y. H. Choi, D. H. Youn, J. S. Lee, Chem. Commun., 2016, 52, 14302-14305.
[23]	E. H. Kim, Y. H. Choi, M. H. Lee, J. Kim, H. B. Kim, K. Y. Kim, E. C. Ra, J. H. Lee, J. S. Lee, J. Catal., 2021, 396, 395-401.
[24]	M. M. Millet, G. Algara-Siller, S. Wrabetz, A. Mazheika, F. Girgsdies, D. Teschner, F. Seitz, A. Tarasov, S. V. Levchenko, R. Schlogl, E. Frei, J. Am. Chem. Soc., 2019, 141, 2451-2461.
[25]	X. Ye, C. Yang, X. Pan, J. Ma, Y. Zhang, Y. Ren, X. Liu, L. Li, Y. Huang, J. Am. Chem. Soc., 2020, 142, 19001-19005.
[26]	F. J. Caparrós, L. Soler, M. D. Rossell, I. Angurell, L. Piccolo, O. Rossell, J. Llorca, ChemCatChem, 2018, 2365-2369.
[27]	L. Kuai, Z. Chen, S. Liu, E. Kan, N. Yu, Y. Ren, C. Fang, X. Li, Y. Li, B. Geng, Nat. Commun., 2020, 11, 48.
[28]	J. H. Kwak, L. Kovarik, J. N. Szanyi, ACS Catal., 2013, 3, 2094-2100.
[29]	Z. Chen, S. Mitchell, E. Vorobyeva, R. K. Leary, R. Hauert, T. Furnival, Q. M. Ramasse, J. M. Thomas, P. A. Midgley, D. Dontsova, Adv. Funct. Mater., 2017, 27, 1605785.
[30]	N. Fu, X. Liang, Z. Li, W. Chen, Y. Wang, L. Zheng, Q. Zhang, C. Chen, D. Wang, Q. Peng, Nano Res., 2020, 13, 947-951.
[31]	H. E. Gottlieb, V. Kotlyar, A. Nudelman, J. Org. Chem., 1997, 62, 7512-7515.
[32]	M. Brun, A. Berthet, J. Bertolini, J. Electron. Spectrosc. Relat. Phenom., 1999, 104, 55-60.
[33]	M. C. Militello, S. J. Simko, Surf. Sci. Spectra, 1994, 3, 387-394.
[34]	G. Bergeret, P. Gallezot, in: Handbook of Heterogeneous Catalysis, G. Ertl eds., Wiley-VCH, 2008, 738-765.
[35]	C. Mondelli, B. Puertolas, M. Ackermann, Z. Chen, J. Perez-Ramirez, ChemSusChem, 2018, 11, 2859-2869.
[36]	L. T. M. Nguyen, H. Park, M. Banu, J. Y. Kim, D. H. Youn, G. Magesh, W. Y. Kim, J. S. Lee, RSC Adv., 2015, 5, 105560-105566.
[37]	K. Mori, T. Taga, H. Yamashita, ACS Catal., 2017, 7, 3147-3151.
[38]	A. V. Bavykina, E. Rozhko, M. G. Goesten, T. Wezendonk, B. Seoane, F. Kapteijn, M. Makkee, J. Gascon, ChemCatChem, 2016, 8, 2217-2221.
[39]	B. Liu, L. Ye, R. Wang, J. Yang, Y. Zhang, R. Guan, L. Tian, X. Chen, ACS Appl. Mater. Interfaces, 2018, 4001-4009.
[40]	Y. Li, B. Li, D. Zhang, L. Cheng, Q. Xiang, ACS Nano, 2020, 14, 10552-10561.

Synergy between single atoms and nanoclusters of Pd/g-C₃N₄ catalysts for efficient base-free CO₂ hydro-genation to formic acid

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