Surface hydrogen migration significantly promotes electroreduction of acetonitrile to ethylamine

Liu, Z. et al. Tuning the selectivity of catalytic nitriles hydrogenation by structure regulation in atomically dispersed Pd catalysts. Nat. Commun. 12, 6194 (2021). 10.1038/s41467-021-26542-y

[2]

Chandrashekhar, V. G., Baumann, W., Beller, M. & Jagadeesh, R. V. Rajenahally Nickel-catalyzed hydrogenative coupling of nitriles and amines for general amine synthesis. Science 376, 1433–1441 (2022). 10.1126/science.abn7565

[3]

Tang, C. et al. Electrocatalytic hydrogenation of acetonitrile to ethylamine in acid. Nat. Commun. 15, 3233 (2024). 10.1038/s41467-024-47622-9

[4]

Lattice oxygen-mediated electron tuning promotes electrochemical hydrogenation of acetonitrile on copper catalysts

Yanyan Fang, Bo Liu, Chongyang Tang et al.

Nature Communications 2023 10.1038/s41467-023-39558-3

[5]

Xia, R. et al. Electrochemical reduction of acetonitrile to ethylamine. Nat. Commun. 12, 1949 (2021). 10.1038/s41467-021-22291-0

[6]

Wu, Y., Huang, Y., Dai, X. & Shi, F. Alcohol amination catalyzed by copper powder as a self-supported catalyst. ChemSusChem 12, 3185–3191 (2019). 10.1002/cssc.201801877

[7]

Sakuramoto, T., Hirao, T., Tobisu, M. & Moriuchi, T. Oxovanadium(V)‐catalyzed direct amination of allyl alcohols. ChemCatChem 11, 1175–1178 (2019). 10.1002/cctc.201801841

[8]

Platinum‐Catalyzed Direct Amination of Allylic Alcohols with Aqueous Ammonia: Selective Synthesis of Primary Allylamines

Kalpataru Das, Ryozo Shibuya, Yasuhito Nakahara et al.

Angewandte Chemie International Edition 2012 10.1002/anie.201106737

[9]

Bähn, S. et al. The catalytic amination of alcohols. ChemCatChem 3, 1853–1864 (2011). 10.1002/cctc.201100255

[10]

Braos-García, P., García-Sancho, C., Infantes-Molina, A., Rodríguez-Castellón, E. & Jiménez-López, A. Bimetallic Ru/Ni supported catalysts for the gas phase hydrogenation of acetonitrile. Appl. Catal. A Gen. 381, 132–144 (2010). 10.1016/j.apcata.2010.03.061

[11]

Aguirre, A. & Collins, S. E. Insight into the mechanism of acetonitrile hydrogenation in liquid phase on Pt/Al2O3 by ATR-FTIR. Catal. Today 336, 22–32 (2019). 10.1016/j.cattod.2019.04.027

[12]

Roose P., Eller K., Henkes E., Rossbacher R. & H., H. Amines. Aliphatic. Ullmann’s Encyclopedia of Industrial Chemistry (ed. Ley C.) (Wiley–VCH, 2015). 10.1002/14356007.a02_001.pub2

[13]

Zhang, D. et al. Highly efficient electrochemical hydrogenation of acetonitrile to ethylamine for primary amine synthesis and promising hydrogen storage. Chem Catal. 1, 393–406 (2021). 10.1016/j.checat.2021.03.012

[14]

Ao, W. et al. Electrochemical reversible reforming between ethylamine and acetonitrile on heterostructured Pd-Ni(OH)2 Nanosheets. Angew. Chem. Int. Ed. 63, e202307924 (2023).

[15]

Zhang, Y. & Kornienko, N. C≡N triple bond cleavage via transmembrane hydrogenation. Chem Catal. 2, 499–507 (2022). 10.1016/j.checat.2022.02.005

[16]

Advanced analysis of copper X‐ray photoelectron spectra

Mark C. Biesinger

Surface and Interface Analysis 2017 10.1002/sia.6239

[17]

Jiang, Z. T., Thurgate, S. M. & Wilkie, P. Line structure in photoelectron and Auger electron spectra of CuOx/Cu and Cu by Auger photoelectron coincidence spectroscopy (APECS). Surf. Interface Anal. 31, 287–290 (2001). 10.1002/sia.990

[18]

Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Sc, Ti, V, Cu and Zn

Mark C. Biesinger, Leo W.M. Lau, Andrea R. Gerson et al.

Applied Surface Science 2010 10.1016/j.apsusc.2010.07.086

[19]

He, M. et al. Selective Enhancement of methane formation in electrochemical CO2 reduction enabled by a raman-inactive oxygen-containing species on Cu. ACS Catal. 12, 6036–6046 (2022). 10.1021/acscatal.2c00087

[20]

Ma, Z. et al. Atomically dispersed Cu catalysts on sulfide-derived defective Ag nanowires for electrochemical CO2 reduction. ACS Nano 17, 2387–2398 (2023). 10.1021/acsnano.2c09473

[21]

Chen, W. et al. Vacancy‐induced catalytic mechanism for alcohol electrooxidation on nickel‐based electrocatalyst. Angew. Chem. Int. Edit. 63 (2023). 10.1002/anie.202316449

[22]

Chen, W. et al. Deciphering the alternating synergy between interlayer Pt single-atom and NiFe layered double hydroxide for overall water splitting. Energ. Environ. Sci. 14, 6428–6440 (2021). 10.1039/d1ee01395e

[23]

Shinagawa, T., Garcia-Esparza, A. T. & Takanabe, K. Insight on Tafel slopes from a microkinetic analysis of aqueous electrocatalysis for energy conversion. Sci. Rep. 5 (2015). 10.1038/srep13801

[24]

Nakanaga, T., Ito, F., Miyawaki, J., Sugawara, K. & Takeo, H. Observation of the infrared spectra of the NH2-stretching vibration modes of aniline-Arn (n = 1, 2) clusters in a supersonic jet using REMPI. Chem. Phys. Lett. 261, 414–420 (1996). 10.1016/0009-2614(96)00994-3

[25]

Xiao, H., Cheng, T. & Goddard, W. A. III. Atomistic mechanisms underlying selectivities in C1 and C2 products from electrochemical reduction of CO on Cu(111). J. Am. Chem. Soc. 139, 130–136 (2017). 10.1021/jacs.6b06846

[26]

Nie, X., Esopi, M. R., Janik, M. J. & Asthagiri, A. Selectivity of CO2 reduction on copper electrodes: the role of the kinetics of elementary steps. Angew. Chem. Int. Ed. 52, 2459–2462 (2013). 10.1002/anie.201208320

[27]

Ciucci, F. & Chen, C. Analysis of electrochemical impedance spectroscopy data using the distribution of relaxation times: a bayesian and hierarchical bayesian approach. Electrochim. Acta 167, 439–454 (2015). 10.1016/j.electacta.2015.03.123

[28]

Wan, T. H., Saccoccio, M., Chen, C. & Ciucci, F. Influence of the discretization methods on the distribution of relaxation times deconvolution: implementing radial basis functions with DRTtools. Electrochim. Acta 184, 483–499 (2015). 10.1016/j.electacta.2015.09.097

[29]

Effat, M. B. & Ciucci, F. Bayesian and hierarchical bayesian based regularization for deconvolving the distribution of relaxation times from electrochemical impedance spectroscopy data. Electrochim. Acta 247, 1117–1129 (2017). 10.1016/j.electacta.2017.07.050

[30]

Zhuo, Y. et al. Ultrafast room‐temperature synthesis of large‐scale, low‐cost, and highly active Ni-Fe based electrodes toward industrialized seawater oxidation. Adv. Energy Mater. 13 (2023). 10.1002/aenm.202301921

[31]

Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996). 10.1103/physrevb.54.11169

[32]

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set

G. Kresse, J. Furthmüller

Computational Materials Science 1996 10.1016/0927-0256(96)00008-0

[33]

Projector augmented-wave method

P. E. Blöchl

Physical Review B 1994 10.1103/physrevb.50.17953

[34]

Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999). 10.1103/physrevb.59.1758

[35]

Generalized Gradient Approximation Made Simple

John P. Perdew, Kieron Burke, Matthias Ernzerhof

Physical Review Letters 1996 10.1103/physrevlett.77.3865

[36]

Mathew, K., Sundararaman, R., Letchworth-Weaver, K., Arias, T. A. & Hennig, R. G. Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways. J. Chem. Phys. 140, 084106 (2014). 10.1063/1.4865107

[37]

Mathew, K., Kolluru, V. S. C., Mula, S., Steinmann, S. N. & Hennig, R. G. Implicit self-consistent electrolyte model in plane-wave density-functional theory. J. Chem. Phys. 151, 234101 (2019). 10.1063/1.5132354

[38]

Sheppard, D., Xiao, P., Chemelewski, W., Johnson, D. D. & Henkelman, G. A generalized solid-state nudged elastic band method. J. Chem. Phys. 136, 074103 (2012). 10.1063/1.3684549

[39]

A climbing image nudged elastic band method for finding saddle points and minimum energy paths

Graeme Henkelman, Blas P. Uberuaga, Hannes Jónsson

The Journal of Chemical Physics 2000 10.1063/1.1329672

[40]

Heyden, A., Bell, A. T. & Keil, F. J. Efficient methods for finding transition states in chemical reactions: comparison of improved dimer method and partitioned rational function optimization method. J. Chem. Phys. 123, 224101 (2005). 10.1063/1.2104507

[41]

Monkhorst, H. J. & Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 13, 5188–5192 (1976). 10.1103/physrevb.13.5188

[42]

Bhola, K., Varghese, J. J., Dapeng, L., Liu, Y. & Mushrif, S. H. Influence of hubbard U parameter in simulating adsorption and reactivity on CuO: combined theoretical and experimental study. J. Phys. Chem. C 121, 21343–21353 (2017). 10.1021/acs.jpcc.7b05385

[43]

Li, H. et al. C2+ selectivity for CO2 electroreduction on oxidized Cu-based catalysts. J. Am. Chem. Soc. 145, 14335–14344 (2023). 10.1021/jacs.3c03022

[44]

Nørskov, J. K. et al. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J. Phys. Chem. B 108, 17886–17892 (2004). 10.1021/jp047349j

[45]

Wang, V., Xu, N., Liu, J.-C., Tang, G. & Geng, W.-T. VASPKIT: a user-friendly interface facilitating high-throughput computing and analysis using VASP code. Comput. Phys. Commun. 267, 108033 (2021). 10.1016/j.cpc.2021.108033

[46]

Chan, K. & Nørskov, J. K. Electrochemical barriers made simple. J. Phys. Chem. Lett. 6, 2663–2668 (2015). 10.1021/acs.jpclett.5b01043

[47]

Chan, K. & Nørskov, J. K. Potential dependence of electrochemical barriers from ab initio calculations. J. Phys. Chem. Lett. 7, 1686–1690 (2016). 10.1021/acs.jpclett.6b00382

[48]

Liu, X. et al. pH effects on the electrochemical reduction of CO(2) towards C2 products on stepped copper. Nat. Commun. 10, 32 (2019). 10.1038/s41467-018-07970-9

[49]

Tang, M. T., Liu, X., Ji, Y., Norskov, J. K. & Chan, K. Modeling hydrogen evolution reaction kinetics through explicit water–metal interfaces. J. Phys. Chem. C 124, 28083–28092 (2020). 10.1021/acs.jpcc.0c08310

Metrics

12

Citations

49

References

Details

Published: Mar 06, 2025
Vol/Issue: 16(1)
License: View

Authors

Department of Neurology, Beijing Tiantan Hospital (A.J., J. Li, M.W., J. Lin, H.L., X.M., Y.W., Y.P.), Capital Medical University, China.; China National Clinical Research Center for Neurological Diseases, Beijing Tiantan Hospital (A.J., J. Li, M.W., J. Lin, H.L., X.M., Y.W., Y.P.), Capital Medical University, China.

School of e‐Commerce and Logistics Management Henan University of Economics and Law Zhengzhou China

H

Haolei Zhang

Department of Otolaryngology and Head and Neck Surgery, The First Hospital of Hebei Medical University, Shijiazhuang City, China.

Nanjing University

Cite This Article

Yulong Tang, Jiejie Li, Yichao Lin, et al. (2025). Surface hydrogen migration significantly promotes electroreduction of acetonitrile to ethylamine. Nature Communications, 16(1). https://doi.org/10.1038/s41467-025-57462-w

Surface hydrogen migration significantly promotes electroreduction of acetonitrile to ethylamine

You May Also Like