Issue

Vol. 16 (2024)

Boosting Electrochemical Urea Synthesis via Constructing Ordered Pd–Zn Active Pair

https://doi.org/10.1007/s40820-024-01462-w
Weiliang Zhou
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, Guangdong, People’s Republic of China
Chao Feng
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, Guangdong, People’s Republic of China
Xuan Li
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, Guangdong, People’s Republic of China
Xingxing Jiang
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, Guangdong, People’s Republic of China
Lingyan Jing
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, Guangdong, People’s Republic of China
Shuai Qi
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, Guangdong, People’s Republic of China
Qihua Huo
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, Guangdong, People’s Republic of China
Miaoyuan Lv
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, Guangdong, People’s Republic of China
Xinbao Chen
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, Guangdong, People’s Republic of China
Tianchi Huang
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, Guangdong, People’s Republic of China
Jingwen Zhao
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, Guangdong, People’s Republic of China
Na Meng
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, Guangdong, People’s Republic of China
Hengpan Yang
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, Guangdong, People’s Republic of China
Qi Hu
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, Guangdong, People’s Republic of China
Chuanxin He
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, Guangdong, People’s Republic of China

Corresponding Author: Chuanxin He

hecx@szu.edu.cn

Nano-Micro Letters, Vol. 16 (2024), Article Number: 247

Abstract

Electrochemical co-reduction of nitrate (NO3–) and carbon dioxide (CO2) has been widely regarded as a promising route to produce urea under ambient conditions, however the yield rate of urea has remained limited. Here, we report an atomically ordered intermetallic pallium-zinc (PdZn) electrocatalyst comprising a high density of PdZn pairs for boosting urea electrosynthesis. It is found that Pd and Zn are responsible for the adsorption and activation of NO3– and CO2, respectively, and thus the co-adsorption and co-activation NO3– and CO2 are achieved in ordered PdZn pairs. More importantly, the ordered and well-defined PdZn pairs provide a dual-site geometric structure conducive to the key C–N coupling with a low kinetical barrier, as demonstrated on both operando measurements and theoretical calculations. Consequently, the PdZn electrocatalyst displays excellent performance for the co-reduction to generate urea with a maximum urea Faradaic efficiency of 62.78% and a urea yield rate of 1274.42 μg mg–1 h–1, and the latter is 1.5-fold larger than disordered pairs in PdZn alloys. This work paves new pathways to boost urea electrosynthesis via constructing ordered dual-metal pairs.


Highlights:
1 Ordered intermetallic pallium-zinc (PdZn) electrocatalyst comprising a high density of PdZn pairs is synthesized for achieving co-adsorption and co-activation carbon dioxide and nitrate.
2 Both operando measurements and theoretical calculations reveal that the PdZn pairs provide a dual-site geometric structure conducive to the key C–N coupling with a low kinetical barrier.
3 The intermetallic PdZn displays excellent performance for the co-reduction of nitrate (NO3–) and carbon dioxide (CO2) toward urea, with a maximum FEurea of 62.78% at a small potential of – 0.4 V versus RHE.

Keywords

Electrochemical C–N coupling Urea electrosynthesis Intermetallic compounds Geometric structures Active pairs
Zhou, Weiliang, Chao Feng, Xuan Li, Xingxing Jiang, Lingyan Jing, Shuai Qi, Qihua Huo, Miaoyuan Lv, Xinbao Chen, Tianchi Huang, Jingwen Zhao, Na Meng, Hengpan Yang, Qi Hu, and Chuanxin He. 2024. “Boosting Electrochemical Urea Synthesis via Constructing Ordered Pd–Zn Active Pair”. Nano-Micro Letters 16 (July):247. https://doi.org/10.1007/s40820-024-01462-w.
Download Citation
Endnote/Zotero/Mendeley (RIS)
BibTeX
References
  1. C. Chen, X. Zhu, X. Wen, Y. Zhou, L. Zhou et al., Coupling N2 and CO2 in H2O to synthesize urea under ambient conditions. Nat. Chem. 12, 717–724 (2020). https://doi.org/10.1038/s41557-020-0481-9
  2. J. Li, Y. Zhang, K. Kuruvinashetti, N. Kornienko, Construction of C–N bonds from small-molecule precursors through heterogeneous electrocatalysis. Nat. Rev. Chem. 6, 303–319 (2022). https://doi.org/10.1038/s41570-022-00379-5
  3. X. Peng, L. Zeng, D. Wang, Z. Liu, Y. Li et al., Electrochemical C–N coupling of CO2 and nitrogenous small molecules for the electrosynthesis of organonitrogen compounds. Chem. Soc. Rev. 52, 2193–2237 (2023). https://doi.org/10.1039/d2cs00381c
  4. A.J. Martín, T. Shinagawa, J. Pérez-Ramírez, Electrocatalytic reduction of nitrogen: from Haber-Bosch to ammonia artificial leaf. Chem 5, 263–283 (2019). https://doi.org/10.1016/j.chempr.2018.10.010
  5. Y. Zhao, Y. Ding, W. Li, C. Liu, Y. Li et al., Efficient urea electrosynthesis from carbon dioxide and nitrate via alternating Cu-W bimetallic C–N coupling sites. Nat. Commun. 14, 4491 (2023). https://doi.org/10.1038/s41467-023-40273-2
  6. Y. Wang, S. Xia, J. Zhang, Z. Li, R. Cai et al., Spatial management of CO diffusion on tandem electrode promotes NH2 intermediate formation for efficient urea electrosynthesis. ACS Energy Lett. 8, 3373–3380 (2023). https://doi.org/10.1021/acsenergylett.3c00824
  7. C. Lv, L. Zhong, H. Liu, Z. Fang, C. Yan et al., Selective electrocatalytic synthesis of urea with nitrate and carbon dioxide. Nat. Sustain. 4, 868–876 (2021). https://doi.org/10.1038/s41893-021-00741-3
  8. M. Yuan, J. Chen, H. Zhang, Q. Li, L. Zhou et al., Host–guest molecular interaction promoted urea electrosynthesis over a precisely designed conductive metal–organic framework. Energy Environ. Sci. 15, 2084–2095 (2022). https://doi.org/10.1039/d1ee03918k
  9. D. Wang, C. Chen, S. Wang, Defect engineering for advanced electrocatalytic conversion of nitrogen-containing molecules. Sci. China Chem. 66, 1052–1072 (2023). https://doi.org/10.1007/s11426-022-1419-y
  10. X. Zhang, X. Zhu, S. Bo, C. Chen, K. Cheng et al., Electrocatalytic urea synthesis with 63.5% faradaic efficiency and 100% N-Selectivity via one-step C–N coupling. Angew. Chem. Int. Ed. 62, e202305447 (2023). https://doi.org/10.1002/anie.202305447
  11. Y. Gao, J. Wang, Y. Yang, J. Wang, C. Zhang et al., Engineering spin states of isolated copper species in a metal-organic framework improves urea electrosynthesis. Nano-Micro Lett. 15, 158 (2023). https://doi.org/10.1007/s40820-023-01127-0
  12. J. Leverett, T. Tran-Phu, J.A. Yuwono, P. Kumar, C. Kim et al., Tuning the coordination structure of Cu–N–C single atom catalysts for simultaneous electrochemical reduction of CO2 and NO3– to urea. Adv. Energy Mater. 12, 2201500 (2022). https://doi.org/10.1002/aenm.202201500
  13. X. Wei, X. Wen, Y. Liu, C. Chen, C. Xie et al., Oxygen vacancy-mediated selective C–N coupling toward electrocatalytic urea synthesis. J. Am. Chem. Soc. 144, 11530–11535 (2022). https://doi.org/10.1021/jacs.2c03452
  14. Q. Zhao, X. Lu, Y. Wang, S. Zhu, Y. Liu et al., Sustainable and high-rate electrosynthesis of nitrogen fertilizer. Angew. Chem. Int. Ed. 62, e20230712310 (2023). https://doi.org/10.1002/anie.202307123
  15. T. Hou, J. Ding, H. Zhang, S. Chen, Q. Liu et al., FeNi3 nanops for electrocatalytic synthesis of urea from carbon dioxide and nitrate. Mater. Chem. Front. 7, 4952–4960 (2023). https://doi.org/10.1039/d3qm00627a
  16. M. Yuan, J. Chen, Y. Bai, Z. Liu, J. Zhang et al., Unveiling electrochemical urea synthesis by co-activation of CO2 and N2 with Mott-Schottky heterostructure catalysts. Angew. Chem. Int. Ed. 60, 10910–10918 (2021). https://doi.org/10.1002/anie.202101275
  17. Y. Liu, X. Tu, X. Wei, D. Wang, X. Zhang et al., C-bound or O-bound surface: which one boosts electrocatalytic urea synthesis? Angew. Chem. Int. Ed. 62, e202300387 (2023). https://doi.org/10.1002/anie.202300387
  18. C. Lv, C. Lee, L. Zhong, H. Liu, J. Liu et al., A defect engineered electrocatalyst that promotes high-efficiency urea synthesis under ambient conditions. Nano Lett. 16, 8213–8222 (2022). https://doi.org/10.1021/acsnano.2c01956
  19. D. Wu, R. Feng, C. Xu, P.-F. Sui, J. Zhang et al., Regulating the electron localization of metallic bismuth for boosting CO2 electroreduction. Nano-Micro Lett. 14, 38 (2021). https://doi.org/10.1007/s40820-021-00772-7
  20. B. Rhimi, M. Zhou, Z. Yan, X. Cai, Z. Jiang, Cu-based materials for enhanced C2+ product selectivity in photo-/ electro-catalytic CO2 reduction: challenges and prospects. Nano-Micro Lett. 16, 64 (2024). https://doi.org/10.1007/s40820-023-01276-2
  21. X.-Y. Ji, K. Sun, Z.-K. Liu, X. Liu, W. Dong et al., Identification of dynamic active sites among Cu species derived from MOFs@CuPc for electrocatalytic nitrate reduction reaction to ammonia. Nano-Micro Lett. 15, 110 (2023). https://doi.org/10.1007/s40820-023-01091-9
  22. C.S. Gerke, Y. Xu, Y. Yang, G.D. Foley, B. Zhang et al., Electrochemical C–N bond formation within boron imidazolate cages featuring single copper sites. J. Am. Chem. Soc. 145, 26144–26151 (2023). https://doi.org/10.1021/jacs.3c08359
  23. S. Chen, G. Qi, R. Yin, Q. Liu, L. Feng et al., Electrocatalytic nitrate-to-ammonia conversion on CoO/CuO nanoarrays using Zn-nitrate batteries. Nanoscale 15, 19577–19585 (2023). https://doi.org/10.1039/d3nr05254k
  24. R. He, N. Xu, I.M.U. Hasan, L. Peng, L. Li et al., Advances in electrolyzer design and development for electrochemical CO2 reduction. EcoMat. 5, e12346 (2023). https://doi.org/10.1002/eom2.12346
  25. S. Zhang, J. Geng, Z. Zhao, M. Jin, W. Li et al., High-efficiency electrosynthesis of urea over bacterial cellulose regulated Pd–Cu bimetallic catalyst. EES. Catal. 1, 45–53 (2023). https://doi.org/10.1039/D2EY00038E
  26. N. Meng, X. Ma, C. Wang, Y. Wang, R. Yang et al., Oxide-derived core-shell Cu@Zn nanowires for urea electrosynthesis from carbon dioxide and nitrate in water. Nano lett. 16, 9095–9104 (2022). https://doi.org/10.1021/acsnano.2c01177
  27. H. Wang, Y. Jiang, S. Li, F. Gou, X. Liu et al., Realizing efficient C–N coupling via electrochemical co-reduction of CO2 and NO3- on AuPd nanoalloy to form urea: key C–N coupling intermediates. Appl. Catal. B Environ. 318, 121819 (2022). https://doi.org/10.1016/j.apcatb.2022.121819
  28. H. Wan, X. Wang, L. Tan, M. Filippi, P. Strasser et al., Electrochemical synthesis of urea: co-reduction of nitric oxide and carbon monoxide. ACS Catal. 13, 1926–1933 (2023). https://doi.org/10.1021/acscatal.2c05315
  29. X. Liu, Y. Jiao, Y. Zheng, M. Jaroniec, S.-Z. Qiao, Mechanism of C–N bonds formation in electrocatalytic urea production revealed by ab initio molecular dynamics simulation. Nat. Commun. 13, 5471 (2022). https://doi.org/10.1038/s41467-022-33258-0
  30. X. Zhang, X. Zhu, S. Bo, C. Chen, M. Qiu et al., Identifying and tailoring C–N coupling site for efficient urea synthesis over diatomic Fe–Ni catalyst. Nat. Commun. 13, 5337 (2022). https://doi.org/10.1038/s41467-022-33066-6
  31. S. Zhang, Y. Zha, Y. Ye, K. Li, Y. Lin et al., Oxygen-coordinated single Mn sites for efficient electrocatalytic nitrate reduction to ammonia. Nano-Micro Lett. 16, 9 (2023). https://doi.org/10.1007/s40820-023-01217-z
  32. X. Rao, J. Yan, K. Yokoyama, X. Shao, C. Inoue et al., A porous Co3O4-carbon paper electrode enabling nearly 100% electrocatalytic reduction of nitrate to ammonia. Mater. Rep. Energy 3, 100216 (2023). https://doi.org/10.1016/j.matre.2023.100216
  33. B. Xu, I.M.U. Hasan, L. Peng, J. Liu, N. Xu et al., Anion-regulation engineering toward Cu/In/MOF bimetallic electrocatalysts for selective electrochemical reduction of CO2 to CO/formate. Mater Rep Energy. 2, 100139 (2022). https://doi.org/10.1016/j.matre.2022.100139
  34. L. Peng, C. Chen, R. He, N. Xu, J. Qiao et al., Tin-doped bismuth dendrites for highly efficient electrocatalytic reduction of CO2 by using bipolar membrane in ultrathin liquid reactor. EcoMat 4, e12260 (2022). https://doi.org/10.1002/eom2.12260
  35. L. Peng, Y. Zhang, R. He, N. Xu, J. Qiao, Research advances in electrocatalysts, electrolytes, reactors and membranes for the electrocatalytic carbon dioxide reduction reaction. Acta Phys. Chim. Sin. (2023). https://doi.org/10.3866/pku.whxb202302037
  36. J. Yan, Y. Guan, B. Marchetti, Y. Liu, F. Ning et al., Bi-Eu bimetallic catalysts enabling ultrastable electroreduction of CO2 with a ∼ 100% formate Faradaic efficiency. Chem. Eng. J. 467, 143531 (2023). https://doi.org/10.1016/j.cej.2023.143531
  37. M. Yang, G. Meng, H. Li, T. Wei, Q. Liu et al., Bifunctional bimetallic oxide nanowires for high-efficiency electrosynthesis of 2, 5-furandicarboxylic acid and ammonia. J. Colloid Interface Sci. 652, 155–163 (2023). https://doi.org/10.1016/j.jcis.2023.08.079
  38. Y. Ji, Z. Chen, R. Wei, C. Yang, Y. Wang et al., Selective CO-to-acetate electroreduction via intermediate adsorption tuning on ordered Cu–Pd sites. Nat. Catal. 5, 251–258 (2022). https://doi.org/10.1038/s41929-022-00757-8
  39. J. Geng, S. Ji, M. Jin, C. Zhang, M. Xu et al., Ambient electrosynthesis of urea with nitrate and carbon dioxide over iron-based dual-sites. Angew. Chem. Int. Ed. 62, e202210958 (2023). https://doi.org/10.1002/anie.202210958
  40. Y. Li, Y. Li, H. Sun, L. Gao, X. Jin et al., Current status and perspectives of dual-atom catalysts towards sustainable energy utilization. Nano-Micro Lett. 16, 139 (2024). https://doi.org/10.1007/s40820-024-01347-y
  41. C.-L. Yang, L.-N. Wang, P. Yin, J. Liu, M.-X. Chen et al., Sulfur-anchoring synthesis of platinum intermetallic nanop catalysts for fuel cells. Science 374, 459–464 (2021). https://doi.org/10.1126/science.abj9980
  42. Y. Yang, W. Xiao, X. Feng, Y. Xiong, M. Gong et al., Golden palladium zinc ordered intermetallics as oxygen reduction electrocatalysts. Nano Lett. 13, 5968–5974 (2019). https://doi.org/10.1021/acsnano.9b01961
  43. W. Xiao, M.A.L. Cordeiro, G. Gao, A. Zheng, J. Wang et al., Atomic rearrangement from disordered to ordered Pd–Fe nanocatalysts with trace amount of Pt decoration for efficient electrocatalysis. Nano Energy 50, 70–78 (2018). https://doi.org/10.1016/j.nanoen.2018.05.032
  44. Q. Gao, B. Yao, H.S. Pillai, W. Zang, X. Han et al., Synthesis of core/shell nanocrystals with ordered intermetallic single-atom alloy layers for nitrate electroreduction to ammonia. Nat. Synth. 2, 624–634 (2023). https://doi.org/10.1038/s44160-023-00258-x
  45. J. Lim, C.-Y. Liu, J. Park, Y.-H. Liu, T.P. Senftle et al., Structure sensitivity of Pd facets for enhanced electrochemical nitrate reduction to ammonia. ACS Catal. 11, 7568–7577 (2021). https://doi.org/10.1021/acscatal.1c01413
  46. W. Luo, J. Zhang, M. Li, A. Züttel, Boosting CO production in electrocatalytic CO2 reduction on highly porous Zn catalysts. ACS Catal. 9, 3783–3791 (2019). https://doi.org/10.1021/acscatal.8b05109
  47. J. Rosen, G.S. Hutchings, Q. Lu, R.V. Forest, A. Moore et al., Electrodeposited Zn dendrites with enhanced CO selectivity for electrocatalytic CO2 reduction. ACS Catal. 5, 4586–4591 (2015). https://doi.org/10.1021/acscatal.5b00922
  48. Y. Guo, R. Zhang, S. Zhang, Y. Zhao, Q. Yang et al., Pd doping-weakened intermediate adsorption to promote electrocatalytic nitrate reduction on TiO2 nanoarrays for ammonia production and energy supply with zinc–nitrate batteries. Energy Environ. Sci. 14, 3938–3944 (2021). https://doi.org/10.1039/D1EE00806D
  49. M. Hu, S. Zhao, S. Liu, C. Chen, W. Chen et al., MOF-confined sub-2 nm atomically ordered intermetallic PdZn nanops as high-performance catalysts for selective hydrogenation of acetylene. Adv. Mater. 30, e1801878 (2018). https://doi.org/10.1002/adma.201801878
  50. X. Tu, X. Zhu, S. Bo, X. Zhang, R. Miao et al., A universal approach for sustainable urea synthesis via intermediate assembly at the electrode/electrolyte interface. Angew. Chem. Int. Ed. 63, e202317087 (2024). https://doi.org/10.1002/anie.202317087
  51. Y. Huang, Y. Wang, Y. Liu, A. Ma, J. Gui et al., Unveiling the quantification minefield in electrocatalytic urea synthesis. Chem. Eng. J. 453, 139836 (2023). https://doi.org/10.1016/j.cej.2022.139836
  52. Q. Hu, K. Gao, X. Wang, H. Zheng, J. Cao et al., Subnanometric Ru clusters with upshifted D band center improve performance for alkaline hydrogen evolution reaction. Nat. Commun. 13, 3958 (2022). https://doi.org/10.1038/s41467-022-31660-2
  53. D. Zhang, Y. Xue, X. Zheng, C. Zhang, Y. Li, Multi-heterointerfaces for selective and efficient urea production. Natl. Sci. Rev. 10, nwac209 (2022). https://doi.org/10.1093/nsr/nwac209
  54. S. Zhu, B. Jiang, W.-B. Cai, M. Shao, Direct observation on reaction intermediates and the role of bicarbonate anions in CO2 electrochemical reduction reaction on Cu surfaces. J. Am. Chem. Soc. 139, 15664–15667 (2017). https://doi.org/10.1021/jacs.7b10462
  55. Y. Huang, R. Yang, C. Wang, N. Meng, Y. Shi et al., Direct electrosynthesis of urea from carbon dioxide and nitric oxide. ACS Energy Lett. 7, 284–291 (2022). https://doi.org/10.1021/acsenergylett.1c02471
  56. N. Meng, Y. Huang, Y. Liu, Y. Yu, B. Zhang, Electrosynthesis of urea from nitrite and CO2 over oxygen vacancy-rich ZnO porous nanosheets. Cell Rep. Phys. Sci. 2, 100378 (2021). https://doi.org/10.1016/j.xcrp.2021.100378
  57. M. Sun, G. Wu, J. Jiang, Y. Yang, A. Du et al., Carbon-anchored molybdenum oxide nanoclusters as efficient catalysts for the electrosynthesis of ammonia and urea. Angew. Chem. Int. Ed. 62, e202301 957 (2023). https://doi.org/10.1002/anie.202301957
  58. M. Yuan, H. Zhang, Y. Xu, R. Liu, R. Wang et al., Artificial frustrated Lewis pairs facilitating the electrochemical N2 and CO2 conversion to urea. Chem Catal. 2, 309–320 (2022). https://doi.org/10.1016/j.checat.2021.11.009
  59. X. Liu, P.V. Kumar, Q. Chen, L. Zhao, F. Ye et al., Carbon nanotubes with fluorine-rich surface as metal-free electrocatalyst for effective synthesis of urea from nitrate and CO2. Appl. Catal. B Environ. 316, 121618 (2022). https://doi.org/10.1016/j.apcatb.2022.121618
  60. M. Yuan, J. Chen, Y. Bai, Z. Liu, J. Zhang et al., Electrochemical C–N coupling with perovskite hybrids toward efficient urea synthesis. Chem. Sci. 12, 6048–6058 (2021). https://doi.org/10.1039/D1SC01467F
  61. Q. Hu, Y. Qin, X. Wang, Z. Wang, X. Huang et al., Reaction intermediate-mediated electrocatalyst synthesis favors specified facet and defect exposure for efficient nitrate–ammonia conversion. Energy Environ. Sci. 14, 4989–4997 (2021). https://doi.org/10.1039/D1EE01731D
  62. Z. Chen, T. Wang, B. Liu, D. Cheng, C. Hu et al., Grain-boundary-rich copper for efficient solar-driven electrochemical CO2 reduction to ethylene and ethanol. J. Am. Chem. Soc. 142, 6878–6883 (2020). https://doi.org/10.1021/jacs.0c00971
Read More
Author biographies are not available.
Download this PDF file
PDF SUPPLEMENTARY FILE
Statistic
Read Counter : 2289 Download : 1692

Most read articles by the same author(s)