% IMPORTANT: The following is UTF-8 encoded. This means that in the presence
% of non-ASCII characters, it will not work with BibTeX 0.99 or older.
% Instead, you should use an up-to-date BibTeX implementation like “bibtex8” or
% “biber”.
@ARTICLE{Agharezaei:1024354,
author = {Agharezaei, Parastoo and Tomohiro, Noguchi Goroh and
Kobayashi, Hirokazu and Schlenz, Hartmut and Yamauchi, Miho
and Ghuman, Kulbir Kaur},
title = {{U}nraveling the {E}nhanced {N} 2 {A}ctivity on {C}u{N}i
{A}lloy {C}atalysts for {A}mmonia {P}roduction:
{E}xperiments, {DFT}, and {S}tatistical {A}nalysis},
journal = {The journal of physical chemistry / C},
volume = {128},
number = {9},
issn = {1932-7447},
address = {Washington, DC},
publisher = {Soc.},
reportid = {FZJ-2024-02110},
pages = {3703 - 3717},
year = {2024},
abstract = {One of the main challenges in designing catalysts for
ammonia synthesis is tocreate active sites on the surface of
the catalyst that prefers to reduce the strong N2
moleculedespite its highly stable structure. Binary alloys
have been demonstrated as potential ammoniasynthesis
catalysts in the literature. However, for binary alloys to
be commercially viable, oneneeds to improve their catalytic
activity for N2 reduction by strategically manipulating
theseveral unique active sites present on their surface.
Herein, by using computational tools, wecreated five
different compositions of CuxNi1−x (0.5 ≤ x ≤ 0.9)
alloys via special quasi-randomstructure (SQS) and genetic
algorithm (GA). The alloy with about $50\%$ of Cu and $50\%$
of Ni ispredicted to have the highest catalytic activity
based on the shift of the d-band center towardthe Fermi
level. We then synthesized MgO-supported Cu0.5Ni0.5
nanoparticles and comparedtheir activity for ammonia
synthesis with that of Ni/MgO and Cu/MgO. It was found that
theMgO-supported Cu0.5Ni0.5 alloy possesses 21 times higher
activity than Cu/MgO and 3 timeshigher than Ni/MgO for
ammonia synthesis, confirming the computational results.
Todemonstrate the impact of alloying on the catalytic
activity, we further investigated all thepossible unique
sites on the surface of the Cu0.5Ni0.5 alloy for nitrogen
reduction reaction (NRR) via density functional theory(DFT).
The investigation of the 96 unique active sites on the
Cu0.5Ni0.5 surface demonstrated that the position and
concentration ofNi atoms near each investigated adsorption
site have a linear correlation with the adsorption energy of
the N2. Along with thestructural and electronic properties
of the active sites modified by Ni, orientation of the N2
molecule also plays an important role indetermining the
activity of the CuNi catalyst. These findings not only
explained the notable increase in the activity of CuNi
catalystscompared to the pure metals for NH3 synthesis but
also offered critical insights required to tailor the
specific surface environment ofCuNi catalysts for NRR. This
knowledge can serve as a foundation for further developments
in designing binary alloy catalysts forsustainable ammonia
synthesis.},
cin = {IEK-1},
ddc = {530},
cid = {I:(DE-Juel1)IEK-1-20101013},
pnm = {1232 - Power-based Fuels and Chemicals (POF4-123)},
pid = {G:(DE-HGF)POF4-1232},
typ = {PUB:(DE-HGF)16},
UT = {WOS:001173697100001},
doi = {10.1021/acs.jpcc.3c06417},
url = {https://juser.fz-juelich.de/record/1024354},
}