Electrocatalysis provides a potential solution to pollution in wastewater by converting it to innocuous N2 gas. However, materials with excellent catalytic activity are typically limited to expensive precious metals, hindering their commercial viability. In response to this challenge, we have conducted the most extensive computational search to date for electrocatalysts that can facilitate reduction reaction, starting with 59 390 candidate bimetallic alloys from the Materials Project and Automatic-Flow databases. Using a joint machine learning- and computation-based screening strategy, we evaluated our candidates based on corrosion resistance, catalytic activity, N2 selectivity, cost, and the ability to synthesize. We found that only 20 materials will satisfy all criteria in our screening strategy, all of which contain varying amounts of Cu. Our proposed list of candidates is consistent with previous materials investigated in the literature, with the exception of Cu–Co and Cu–Ag based compounds that merit further investigation.
REFERENCES
1.
D.
Xu
, Y.
Li
, L.
Yin
, Y.
Ji
, J.
Niu
, and Y.
Yu
, “Electrochemical removal of nitrate in industrial wastewater
,” Front. Environ. Sci. Eng.
12
, 9
(2018
).2.
R.
Carrey
, E.
Ballesté
, A. R.
Blanch
, F.
Lucena
, P.
Pons
, J. M.
López
, M.
Rull
, J.
Solà
, N.
Micola
, J.
Fraile
et al., “Combining multi-isotopic and molecular source tracking methods to identify nitrate pollution sources in surface and groundwater
,” Water Res.
188
, 116537
(2021
).3.
Q.
Yi
, Y.
Zhang
, K.
Xie
, Q.
Chen
, F.
Zheng
, D.
Tonina
, W.
Shi
, and C.
Chen
, “Tracking nitrogen pollution sources in plain watersheds by combining high-frequency water quality monitoring with tracing dual nitrate isotopes
,” J. Hydrol.
581
, 124439
(2020
).4.
P. M.
Vitousek
, J. D.
Aber
, R. W.
Howarth
, G. E.
Likens
, P. A.
Matson
, D. W.
Schindler
, W. H.
Schlesinger
, and D. G.
Tilman
, “Human alteration of the global nitrogen cycle: Sources and consequences
,” Ecol. Appl.
7
, 737
–750
(1997
).5.
R.
Epsztein
, O.
Nir
, O.
Lahav
, and M.
Green
, “Selective nitrate removal from groundwater using a hybrid nanofiltration–reverse osmosis filtration scheme
,” Chem. Eng. J.
279
, 372
–378
(2015
).6.
L. N.
Pincus
, H. E.
Rudel
, P. V.
Petrović
, S.
Gupta
, P.
Westerhoff
, C. L.
Muhich
, and J. B.
Zimmerman
, “Exploring the mechanisms of selectivity for environmentally significant oxo-anion removal during water treatment: A review of common competing oxo-anions and tools for quantifying selective adsorption
,” Environ. Sci. Technol.
54
, 9769
–9790
(2020
).7.
S.
Samatya
, N.
Kabay
, Ü.
Yüksel
, M.
Arda
, and M.
Yüksel
, “Removal of nitrate from aqueous solution by nitrate selective ion exchange resins
,” React. Funct. Polym.
66
, 1206
–1214
(2006
).8.
G. K.
Luk
and W. C.
Au-Yeung
, “Experimental investigation on the chemical reduction of nitrate from groundwater
,” Adv. Environ. Res.
6
, 441
–453
(2002
).9.
S.
Guo
, K.
Heck
, S.
Kasiraju
, H.
Qian
, Z.
Zhao
, L. C.
Grabow
, J. T.
Miller
, and M. S.
Wong
, “Insights into nitrate reduction over indium-decorated palladium nanoparticle catalysts
,” ACS Catal.
8
, 503
–515
(2018
).10.
J.
Radjenovic
and D. L.
Sedlak
, “Challenges and opportunities for electrochemical processes as next-generation technologies for the treatment of contaminated water
,” Environ. Sci. Technol.
49
, 11292
–11302
(2015
).11.
M. I. M.
Soares
, “Biological denitrification of groundwater
,” Water, Air, Soil Pollut.
123
, 183
–193
(2000
).12.
P. M.
Ayyasamy
, K.
Shanthi
, P.
Lakshmanaperumalsamy
, S.-J.
Lee
, N.-C.
Choi
, and D.-J.
Kim
, “Two-stage removal of nitrate from groundwater using biological and chemical treatments
,” J. Biosci. Bioeng.
104
, 129
–134
(2007
).13.
F.
Rezvani
, M.-H.
Sarrafzadeh
, S.
Ebrahimi
, and H.-M.
Oh
, “Nitrate removal from drinking water with a focus on biological methods: A review
,” Environ. Sci. Pollut. Res.
26
, 1124
–1141
(2019
).14.
15.
C. J.
Werth
, C.
Yan
, and J. P.
Troutman
, “Factors impeding replacement of ion exchange with (electro)catalytic treatment for nitrate removal from drinking water
,” ACS EST Eng.
1
, 6
–20
(2021
).16.
W.
Duan
, G.
Li
, Z.
Lei
, T.
Zhu
, Y.
Xue
, C.
Wei
, and C.
Feng
, “Highly active and durable carbon electrocatalyst for nitrate reduction reaction
,” Water Res.
161
, 126
–135
(2019
).17.
M.
Paidar
, I.
Roušar
, and K.
Bouzek
, “Electrochemical removal of nitrate ions in waste solutions after regeneration of ion exchange columns
,” J. Appl. Electrochem.
29
, 611
–617
(1999
).18.
J.
Martínez
, A.
Ortiz
, and I.
Ortiz
, “State-of-the-art and perspectives of the catalytic and electrocatalytic reduction of aqueous nitrates
,” Appl. Catal., B
207
, 42
–59
(2017
).19.
G. E.
Dima
, A. C. A.
De Vooys
, and M. T. M.
Koper
, “Electrocatalytic reduction of nitrate at low concentration on coinage and transition-metal electrodes in acid solutions
,” J. Electroanal. Chem.
554–555
, 15
–23
(2003
).20.
Z.
Shen
, D.
Liu
, G.
Peng
, Y.
Ma
, J.
Li
, J.
Shi
, J.
Peng
, and L.
Ding
, “Electrocatalytic reduction of nitrate in water using Cu/Pd modified Ni foam cathode: High nitrate removal efficiency and N2-selectivity
,” Sep. Purif. Technol.
241
, 116743
(2020
).21.
Metalary—Latest and Historical Metal Prices, www.metalary.com,
2016
.22.
A. K.
Singh
, J. H.
Montoya
, J. M.
Gregoire
, and K. A.
Persson
, “Robust and synthesizable photocatalysts for CO2 reduction: A data-driven materials discovery
,” Nat. Commun.
10
, 443
(2019
).23.
K.
Abdelfatah
, W.
Yang
, R.
Vijay Solomon
, B.
Rajbanshi
, A.
Chowdhury
, M.
Zare
, S. K.
Kundu
, A.
Yonge
, A.
Heyden
, and G.
Terejanu
, “Prediction of transition-state energies of hydrodeoxygenation reactions on transition-metal surfaces based on machine learning
,” J. Phys. Chem. C
123
, 29804
–29810
(2019
).24.
D.
Roy
, S. C.
Mandal
, and B.
Pathak
, “Machine learning-driven high-throughput screening of alloy-based catalysts for selective CO2 hydrogenation to methanol
,” ACS Appl. Mater. Interfaces
13
, 56151
(2021
).25.
A.
Malek
, Q.
Wang
, S.
Baumann
, O.
Guillon
, M.
Eikerling
, and K.
Malek
, “A data-driven framework for the accelerated discovery of CO2 reduction electrocatalysts
,” Front. Energy Res.
9
, 609070
(2021
).26.
G. H.
Gu
, J.
Noh
, S.
Kim
, S.
Back
, Z.
Ulissi
, and Y.
Jung
, “Practical deep-learning representation for fast heterogeneous catalyst screening
,” J. Phys. Chem. Lett.
11
, 3185
–3191
(2020
).27.
J.
Schumann
, A. J.
Medford
, J. S.
Yoo
, Z.-J.
Zhao
, P.
Bothra
, A.
Cao
, F.
Studt
, F.
Abild-Pedersen
, and J. K.
Nørskov
, “Selectivity of synthesis gas conversion to C2+ oxygenates on fcc(111) transition-metal surfaces
,” ACS Catal.
8
, 3447
–3453
(2018
).28.
T.
Wang
, G.
Li
, X.
Cui
, and F.
Abild-Pedersen
, “Identification of earth-abundant materials for selective dehydrogenation of light alkanes to olefins
,” Proc. Natl. Acad. Sci. U. S. A.
118
, e2024666118
(2021
).29.
S.
Wang
, N.
Omidvar
, E.
Marx
, and H.
Xin
, “Coordination numbers for unraveling intrinsic size effects in gold-catalyzed CO oxidation
,” Phys. Chem. Chem. Phys.
20
, 6055
–6059
(2018
).30.
Y.
Song
and L. C.
Grabow
, “Activity trends for catalytic CO and NO Co-oxidation at low temperature diesel emission conditions
,” Ind. Eng. Chem. Res.
57
, 12715
–12725
(2018
).31.
K. S.
Exner
, I.
Sohrabnejad-Eskan
, and H.
Over
, “A universal approach to determine the free energy diagram of an electrocatalytic reaction
,” ACS Catal.
8
, 1864
–1879
(2018
).32.
J.-X.
Liu
, D.
Richards
, N.
Singh
, and B. R.
Goldsmith
, “Activity and selectivity trends in electrocatalytic nitrate reduction on transition metals
,” ACS Catal.
9
, 7052
–7064
(2019
).33.
Z.
Wang
, S. D.
Young
, B. R.
Goldsmith
, and N.
Singh
, “Increasing electrocatalytic nitrate reduction activity by controlling adsorption through PtRu alloying
,” J. Catal.
395
, 143
–154
(2021
).34.
L.
Chanussot
, A.
Das
, S.
Goyal
, T.
Lavril
, M.
Shuaibi
, M.
Riviere
, K.
Tran
, J.
Heras-Domingo
, C.
Ho
, W.
Hu
, A.
Palizhati
, A.
Sriram
, B.
Wood
, J.
Yoon
, D.
Parikh
, C. L.
Zitnick
, and Z.
Ulissi
, “Open catalyst 2020 (OC20) dataset and community challenges
,” ACS Catal.
11
, 6059
–6072
(2021
); arXiv:2010.09990.35.
W. L.
Hamilton
, R.
Ying
, and J.
Leskovec
, “Representation learning on graphs: Methods and applications
,” in IEEE Data Engineering Bulletin
, 2017
.36.
A.
Jain
, S. P.
Ong
, G.
Hautier
, W.
Chen
, W. D.
Richards
, S.
Dacek
, S.
Cholia
, D.
Gunter
, D.
Skinner
, G.
Ceder
et al., “Commentary: The materials project: A materials genome approach to accelerating materials innovation
,” APL Mater.
1
, 011002
(2013
).37.
S.
Curtarolo
, W.
Setyawan
, G. L. W.
Hart
, M.
Jahnatek
, R. V.
Chepulskii
, R. H.
Taylor
, S.
Wang
, J.
Xue
, K.
Yang
, O.
Levy
et al., “AFLOW: An automatic framework for high-throughput materials discovery
,” Comput. Mater. Sci.
58
, 218
–226
(2012
).38.
J. H.
Montoya
and K. A.
Persson
, “A high-throughput framework for determining adsorption energies on solid surfaces
,” npj Comput. Mater.
3
, 14
(2017
).39.
G.
Kresse
and J.
Furthmüller
, “Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
,” Phys. Rev. B
54
, 11169
–11186
(1996
).40.
G.
Kresse
and J.
Hafner
, “Ab initio molecular dynamics for liquid metals
,” Phys. Rev. B
47
, 558
–561
(1993
).41.
P. E.
Blöchl
, “Projector augmented-wave method
,” Phys. Rev. B
50
, 17953
–17979
(1994
).42.
J. P.
Perdew
, K.
Burke
, and M.
Ernzerhof
, “Generalized gradient approximation made simple
,” Phys. Rev. Lett.
77
, 3865
–3868
(1996
).43.
M.
Methfessel
and A. T.
Paxton
, “High-precision sampling for Brillouin-zone integration in metals
,” Phys. Rev. B
40
, 3616
–3621
(1989
).44.
S. P.
Ong
, W. D.
Richards
, A.
Jain
, G.
Hautier
, M.
Kocher
, S.
Cholia
, D.
Gunter
, V. L.
Chevrier
, K. A.
Persson
, and G.
Ceder
, “Python materials Genomics (pymatgen): A robust, open-source python library for materials analysis
,” Comput. Mater. Sci.
68
, 314
–319
(2013
).45.
W.
Sun
and G.
Ceder
, “Efficient creation and convergence of surface slabs
,” Surf. Sci.
617
, 53
–59
(2013
).46.
X.
Chen
, X.
Huo
, J.
Liu
, Y.
Wang
, C. J.
Werth
, and T. J.
Strathmann
, “Exploring beyond palladium: Catalytic reduction of aqueous oxyanion pollutants with alternative platinum group metals and new mechanistic implications
,” Chem. Eng. J.
313
, 745
–752
(2017
).47.
G. G.
Valiyeva
, I.
Bavasso
, L.
Di Palma
, S. R.
Hajiyeva
, M. A.
Ramazanov
, and F. V.
Hajiyeva
, “Synthesis of Fe/Ni bimetallic nanoparticles and application to the catalytic removal of nitrates from water
,” Nanomaterials
9
, 1130
(2019
).48.
M. A.
Hasnat
, R.
Agui
, S.
Hinokuma
, T.
Yamaguchi
, and M.
Machida
, “Different reaction routes in electrocatalytic nitrate/nitrite reduction using an H+-conducting solid polymer electrolyte
,” Catal. Commun.
10
, 1132
–1135
(2009
).49.
S.
Hamid
, S.
Bae
, and W.
Lee
, “Novel bimetallic catalyst supported by red mud for enhanced nitrate reduction
,” Chem. Eng. J.
348
, 877
–887
(2018
).50.
I.
Witońska
, S.
Karski
, and J.
Gołuchowska
, “Kinetic studies on the hydrogenation of nitrate in water using Rh/Al2O3 and Rh–Cu/Al2O3 catalysts
,” Kinet. Catal.
48
, 823
–828
(2007
).51.
H.
Liu
, Y.
Yu
, W.
Yang
, W.
Lei
, M.
Gao
, and S.
Guo
, “High-density defects on PdAg nanowire networks as catalytic hot spots for efficient dehydrogenation of formic acid and reduction of nitrate
,” Nanoscale
9
, 9305
–9309
(2017
).52.
M. P.
Maia
, M. A.
Rodrigues
, and F. B.
Passos
, “Nitrate catalytic reduction in water using niobia supported palladium–copper catalysts
,” Catal. Today
123
, 171
–176
(2007
).53.
J.
Park
, J. K.
Choe
, W.
Lee
, and S.
Bae
, “Highly fast and selective removal of nitrate in groundwater by bimetallic catalysts supported by fly ash-derived zeolite Na-X
,” Environ. Sci.: Nano
7
, 3360
–3371
(2020
).54.
W.
Siriwatcharapiboon
, Y.
Kwon
, J.
Yang
, R. L.
Chantry
, Z.
Li
, S. L.
Horswell
, and M. T. M.
Koper
, “Promotion effects of Sn on the electrocatalytic reduction of nitrate at Rh nanoparticles
,” ChemElectroChem
1
, 172
–179
(2014
).55.
O. S. G. P.
Soares
, J. J. M.
Órfão
, and M. F. R.
Pereira
, “Bimetallic catalysts supported on activated carbon for the nitrate reduction in water: Optimization of catalysts composition
,” Appl. Catal., B
91
, 441
–448
(2009
).56.
M. A.
Hasnat
, M. R.
Karim
, and M.
Machida
, “Electrocatalytic ammonia synthesis: Role of cathode materials and reactor configuration
,” Catal. Commun.
10
, 1975
–1979
(2009
).57.
L.
Lemaignen
, C.
Tong
, V.
Begon
, R.
Burch
, and D.
Chadwick
, “Catalytic denitrification of water with palladium-based catalysts supported on activated carbons
,” Catal. Today
75
, 43
–48
(2002
).58.
J.
Klicpera
, S.
Giri
, J. T.
Margraf
, and S.
Günnemann
, “Fast and uncertainty-aware directional message passing for non-equilibrium molecules
,” arXiv:2011.14115 (2020
).59.
J.
Klicpera
, J.
Groß
, and S.
Günnemann
, “Directional message passing for molecular graphs
,” in International Conference on Learning Representations (ICLR)
(ICLR
, 2020
), pp. 1
–13
.60.
A. J. R.
Hensley
, K.
Ghale
, C.
Rieg
, T.
Dang
, E. S.
Anderst
, F.
Studt
, C. T.
Campbell
, J.-S.
McEwen
, and Y.
Xu
, “A DFT-based method for more accurate adsorption energies: An adaptive sum of energies from RPBE and vdW density functionals
,” J. Phys. Chem. C
121
, 4937
(2017
).61.
A.
Jain
, Z.
Wang
, and J. K.
Nørskov
, “Stable two-dimensional materials for oxygen reduction and oxygen evolution reactions
,” ACS Energy Lett.
4
, 1410
–1411
(2019
).62.
A. K.
Singh
, L.
Zhou
, A.
Shinde
, S. K.
Suram
, J. H.
Montoya
, D.
Winston
, J. M.
Gregoire
, and K. A.
Persson
, “Electrochemical stability of metastable materials
,” Chem. Mater.
29
, 10159
–10167
(2017
).63.
Daily Metal Price: Free Metal Price Tables and Charts, https://www.dailymetalprice.com/,
2021
.64.
APMEX: Precious Metals Dealer, https://www.apmex.com/,
2021
.65.
M.
Aykol
, S. S.
Dwaraknath
, W.
Sun
, and K. A.
Persson
, “Thermodynamic limit for synthesis of metastable inorganic materials
,” Sci. Adv.
4
, eaaq0148
(2018
).66.
Y.
Wang
, A.
Xu
, Z.
Wang
, L.
Huang
, J.
Li
, F.
Li
, J.
Wicks
, M.
Luo
, D.-H.
Nam
, C.-S.
Tan
, Y.
Ding
, J.
Wu
, Y.
Lum
, C.-T.
Dinh
, D.
Sinton
, G.
Zheng
, and E. H.
Sargent
, “Enhanced nitrate-to-ammonia activity on copper-nickel alloys via tuning of intermediate adsorption
,” J. Am. Chem. Soc.
142
, 5702
–5708
(2020
).67.
X.
Zhang
, Y.
Wang
, C.
Liu
, Y.
Yu
, S.
Lu
, and B.
Zhang
, “Recent advances in non-noble metal electrocatalysts for nitrate reduction
,” Chem. Eng. J.
403
, 126269
(2021
).68.
N.
Comisso
, S.
Cattarin
, S.
Fiameni
, R.
Gerbasi
, L.
Mattarozzi
, M.
Musiani
, L.
Vázquez-Gómez
, and E.
Verlato
, “Electrodeposition of Cu-Rh alloys and their use as cathodes for nitrate reduction
,” Electrochem. Commun.
25
, 91
–93
(2012
).69.
Y.
Zhang
, Y.
Zhao
, Z.
Chen
, L.
Wang
, L.
Zhou
, P.
Wu
, F.
Wang
, and P.
Ou
, “Fe/Cu composite electrode prepared by electrodeposition and its excellent behavior in nitrate electrochemical removal
,” J. Electrochem. Soci.
165
, E420
–E428
(2018
).70.
L.
Mattarozzi
, S.
Cattarin
, N.
Comisso
, R.
Gerbasi
, P.
Guerriero
, M.
Musiani
, L.
Vázquez-Gómez
, and E.
Verlato
, “Electrodeposition of compact and porous Cu-Zn alloy electrodes and their use in the cathodic reduction of nitrate
,” J. Electrochem. Soc.
162
, D236
–D241
(2015
).71.
L.
Mattarozzi
, S.
Cattarin
, N.
Comisso
, P.
Guerriero
, M.
Musiani
, L.
Vázquez-Gómez
, and E.
Verlato
, “Electrochemical reduction of nitrate and nitrite in alkaline media at CuNi alloy electrodes
,” Electrochim. Acta
89
, 488
–496
(2013
).72.
D.
Reyter
, D.
Bélanger
, and L.
Roué
, “Optimization of the cathode material for nitrate removal by a paired electrolysis process
,” J. Hazard. Mater.
192
, 507
–513
(2011
).73.
B. K.
Simpson
and D. C.
Johnson
, “Electrocatalysis of nitrate reduction at copper-nickel alloy electrodes in acidic media
,” Electroanalysis
16
, 532
–538
(2004
).74.
Y.
Zeng
, C.
Priest
, G.
Wang
, and G.
Wu
, “Restoring the nitrogen cycle by electrochemical reduction of nitrate: Progress and prospects
,” Small Methods
4
, 2000672
(2020
).75.
Z.
Wang
, D.
Richards
, and N.
Singh
, “Recent discoveries in the reaction mechanism of heterogeneous electrocatalytic nitrate reduction
,” Catal.: Sci. Technol.
11
, 705
–725
(2021
).76.
J. M.
McEnaney
, S. J.
Blair
, A. C.
Nielander
, J. A.
Schwalbe
, D. M.
Koshy
, M.
Cargnello
, and T. F.
Jaramillo
, “Electrolyte engineering for efficient electrochemical nitrate reduction to ammonia on a titanium electrode
,” ACS Sustainable Chem. Eng.
8
, 2672
–2681
(2020
).77.
M. T.
De Groot
and M. T. M.
Koper
, “The influence of nitrate concentration and acidity on the electrocatalytic reduction of nitrate on platinum
,” J. Electroanal. Chem.
562
, 81
–94
(2004
).78.
C.
Bing
, Bureau of Reclamation, 2009
.79.
C.
Su
and R. W.
Puls
, “Nitrate reduction by zerovalent iron: Effects of formate, oxalate, citrate, chloride, sulfate, borate, and phosphate
,” Environ. Sci. Technol.
38
, 2715
–2720
(2004
).80.
M. A.
Hasnat
, J. A.
Safwan
, M. A.
Rashed
, Z.
Rahman
, M. M.
Rahman
, Y.
Nagao
, and A. M.
Asiri
, “Inverse effects of supporting electrolytes on the electrocatalytic nitrate reduction activities in a Pt|Nafion|Pt-Cu-type reactor assembly
,” RSC Adv.
6
, 11609
–11617
(2016
).81.
A.
Kulkarni
, S.
Siahrostami
, A.
Patel
, and J. K.
Nørskov
, “Understanding catalytic activity trends in the oxygen reduction reaction
,” Chem. Rev.
118
, 2302
–2312
(2018
).82.
J. K.
Nørskov
, F.
Studt
, F.
Abild-Pederson
, and T.
Bligaard
, Fundamental Concepts in Heterogeneous Catalysis
(John Wiley & Sons
, Hoboken, NJ
, 2014
), p. 196
.83.
Nitrate https://github.com/ulissigroup/nitrate,
2021
.© 2022 Author(s). Published under an exclusive license by AIP Publishing.
2022
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