molecules
Review
Advances in Semiconductor-Based Nanocomposite
Photo(electro)catalysts for Nitrogen Reduction to Ammonia
Cheng Zuo and Qian Su *
Citation: Zuo, C.; Su, Q. Advances in
Semiconductor-Based Nanocomposite
Photo(electro)catalysts for Nitrogen
Reduction to Ammonia. Molecules
2023, 28, 2666. https://doi.org/
10.3390/molecules28062666
Academic Editor: Luísa Margarida
Martins
Received: 12 February 2023
Revised: 5 March 2023
Accepted: 13 March 2023
Published: 15 March 2023
Copyright: © 2023 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Molecules 2023, 28, 2666. https://doi.org/10.3390/molecules28062666
College of Chemical Engineering and Environmental Engineering, Weifang University, Weifang 261061, China
* Correspondence: sqian316@wfu.edu.cn
Abstract: Photo(electro)catalytic nitrogen fixation technology is a promising ammonia synthesis
technology using clean solar and electric energy as the driving energy. Abundant nitrogen and
water as raw materials uphold the principle of green and sustainable development. However, the
generally low efficiency of the nitrogen reduction reaction has seriously restricted the application and
development of this technology. The paper introduces the nitrogen reduction process and discusses
the main challenges and differences in the current photo(electro)catalytic nitrogen fixation systems.
It focuses on promoting the adsorption and activation of N2 and the resolution and diffusion of
NH3 generated. In recent years, reviews of the modification strategies of semiconductor materials in
light of the typical cases of nitrogen fixation have been reported in the literature. Finally, the future
development trend of this field is analyzed and prospected.
Keywords: photocatalyst; electrocatalyst; nitrogen reduction; nanomaterials
1. Introduction
Ammonia is a carbon-free hydrogen storage compound widely used in agriculture,
the chemical industry, medicine, energy storage, and other fields [1]. The ammonia Haber–
Bosch (HB) synthesis process is undoubtedly one of the most important inventions in
modern history and is also the most mature process for the large-scale production of
nitrogen-based fertilizer. The annual output of NH3 reaches 160 million tons, of which
80% is used to produce fertilizer to feed more than 70% of the world’s population. The HB
process uses an iron-doped catalyst to convert N2 and H2 mixed in a 1:3 ratio to ammo-
nia. This process requires reaction conditions of high temperature (400–600 ◦ C) and high
pressure (200–400 atm) to activate the highly stable N≡N (bond dissociation energy up
to 941 kJ·mol−1 ) in the N2 molecule. However, the HB process consumes about 2% of the
world’s total energy annually and emits 300 million tons of CO2 greenhouse gas, accounting
for about 1.6% of global emissions [2]. Therefore, to alleviate energy consumption and en-
vironmental problems, seeking a sustainable and cost-effective ammonia synthesis strategy
is necessary. NH3 synthesis strategies such as biocatalysis, electrocatalysis, and photo-
catalysis have been studied on a laboratory scale. Among them, photo(electro)catalytic
nitrogen reduction synthetic ammonia technology, driven by inexhaustible solar energy,
reduces nitrogen to ammonia with high energy density, easy storage and transportation.
In addition, the nitrogen reduction process can also be carried out under environmental
conditions while achieving zero carbon emissions, which is harmless to the environment. It
is considered a potential alternative to the industrial HB process to generate NH3 , which
has aroused the keen attention of society.
Although the Gibbs free energy of ammonia synthesis is negative, it cannot sponta-
neously react at room temperature and environmental pressure due to the stability and
chemical inertness of N2 . It is an arduous task to convert N2 into NH3 directly. In 1977,
Schrauzer and Guth [3] found that Fe2 O3 -doped TiO2 powder could reduce nitrogen to
ammonia under UV light irradiation. Subsequently, it was reported [4] that desert sands
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Molecules 2023, 28, 2666 2 of 18

formed after weathering titanite-rich rocks could fix nitrogen by photoreaction in 1983.
Tennakone’s group [5] prepared ultrafine Fe(O)OH particles with photocatalytic activity
in reducing nitrogen to ammonia and discussed the preparation method, ammonia yield,
and reaction mechanism of the catalyst in 1991. These landmark events confirmed the
possibility of using solar energy to reduce nitrogen to synthesize ammonia directly and
raised the curtain on the exploration and application of semiconductor materials in the
field of photocatalytic nitrogen fixation. However, the heterogeneous reaction efficiency
in an aqueous solution is low due to the weak adsorption and the activation difficulty
of N2 molecules on the catalyst surface, the participation of high-energy intermediates,
and the complex multi-electron transfer reaction pathway. In addition, the photocatalytic
reduction reaction is affected by the easy recombination of photogenerated electron holes
and the weak reduction ability of photogenerated electrons. The reaction efficiency of
electrocatalysis is limited by high overpotential, low current density, low selectivity, and
competition for hydrogen evolution reactions. Therefore, developing highly active and
stable catalysts is vital in converting N2 to NH3 .
Photo(electro)catalysis has developed rapidly in the past decades, and many differ-
ent types of photo(electro)catalysts have been proposed, including noble metals, metal
complexes, organic molecules, ions, and semiconductors. Since semiconductors offer signif-
icant advantages in manufacturing cost, material toxicity and stability compared to other
situations, they show attractive promise in photocatalysis research and have long been
studied and tested. So far, researchers have designed and developed various semiconductor
photo(electro)catalytic materials, including metal oxides (TiO2 , Fe2 O3 , ZnO) [6–8], metal
sulfides (MoS2 , CdS, ZnS) [9–12], bismuth-based materials (BiOX, X = Cl, Br, I) [13,14],
carbon-based materials (diamond, graphene, g–C3 N4 ) and MOFs. Some progress has
been made in the design optimization of semiconductor materials and their photocat-
alytic nitrogen fixation performance [15]. However, the overall reaction efficiency of the
photo(electro)catalytic nitrogen fixation was still very low. It did not meet the require-
ments of practical applications, so there was an urgent need for breakthroughs in the
knowledge and understanding of fundamental scientific issues. This paper introduces
the process and mechanism of nitrogen reduction and points out the main challenges
of the photo(electro)catalytic nitrogen fixation system. It focuses on the modification
of semiconductor nanomaterials and proposes strategies to enhance the performance of
photo(electro)catalytic nitrogen fixation, summarizing the current status of recent research
on nitrogen reduction. Finally, future research will provide new ideas and inspiration for
the photo(electro)catalytic nitrogen fixation process under mild conditions.

2. Nitrogen Reduction Reaction

Semiconductors generate photogenerated electrons (e− ) and photogenerated holes
(h+ )under UV and visible light excitation. The photogenerated electrons on the conduction
band (CB) reduce N2 to NH3 (N2 + 6H+ + 6e− → 2NH3 ). The photogenerated holes on
the valence band (VB) oxidize H2 O to O2 and provide protons for the reduction reac-
tion (3H2 O + 6h+ → 6H+ + 1.5O2 ), achieving low energy consumption and zero carbon
emissions for the nitrogen reduction reaction (NRR) (Figure 1) [16].
Thermodynamically, whether the photocatalytic reaction could occur depends on the
redox potential of the adsorbate and the position of the energy band of the semiconductor.
In the nitrogen reduction reaction, the semiconductor’s conduction band position should
be higher (more negative) than the nitrogen hydrogenation reduction potential, while the
valence band should be lower (more positive) than the oxygen precipitation potential.
Under the combined effect of light and catalyst, N2 is reduced to NH3 by a series of
photogenerated electrons and water-born proton injection; the hydrogenation reaction
in the process with the corresponding reduction potential [17] was shown in Table 1.
The first electron transfer (Equation (1c)) and proton-coupled electron transfer (Equation
(1d)) processes in the hydrogenation process were high-energy transition states with slow
reaction kinetics that reduced the overall reaction efficiency.
Molecules 2023, 28, x FOR PEER REVIEW 3 of 19
Molecules 2023, 28, 2666 3 of 18

e− e− e−

Figure 1. Schematic illustration of the photocatalytic process of semiconductors.

Table 1. Nitrogen hydrogenation reaction and reduction potentials (vs. NHE at pH = 0).
Thermodynamically, whether the photocatalytic reaction could occur depends on the
redox potential of the adsorbate and
Reaction the position
Reduction of the
Potential (V)energy band of the semiconductor.
Equation
In the nitrogen reduction reaction, the semiconductor’s conduction band position should
H2 O → 1/2O2 + 2H+ + 2e− 0.81 1a
be higher (more negative)
2H+ + 2e− → H2
than the nitrogen hydrogenation
−0.42
reduction potential,
1b
while the
valence Nband −should
2 + e → N2
- be lower (more positive)
−4.16 than the oxygen precipitation
1c potential.
Under N2the + + e− → Neffect
+ Hcombined of light and catalyst,
−3.2 N2 is reduced to NH3 by1d a series of pho-
2H
togenerated + 2e− → Nand
N2 + 2H+ electrons 2 H2 water-born proton−1.10injection; the hydrogenation1ereaction in the
process 4H+ +the
N2 + with 4e−corresponding
→ N2 H4 reduction−potential
0.36 [17] was shown in Table1f 1. The first
N2 + 5H+ + 4e− → N2 H5 + − 0.23 1g
electron transfer (Equation (1c)) and proton-coupled electron transfer (Equation (1d)) pro-
N2 + 6H+ + 6e− → 2N2 H3 0.55 1h
cesses in the hydrogenation
N2 + 8H+ + 8e− → 2N2 H4
process were high-energy
0.27
transition states with
1i
slow reaction
kinetics that reduced the overall reaction efficiency.
The exact mechanism of the nitrogen reduction reaction was ambiguous. Currently,
Table 1. Nitrogen hydrogenation reaction and reduction potentials (vs. NHE at pH = 0).
there are three recognized catalytic hydrogenation mechanisms: dissociation mechanism,
association mechanism
Reaction and enzyme catalytic Reduction mechanism
Potential (Figure
(V) 2) [18].Equation
The dissociation
mechanism refers to
H2O → 1/2O2 + 2H + 2e the + direct
− breaking of the chemical
0.81 bond in the N molecule and
2 1a
the formation2H+ +of2etwo − → isolated
H2 nitrogen atoms −0.42on the catalyst surface, which 1b then under-
goes hydrogenation
N2 + e → N2
− to produce
- NH 3 . The H-B process
−4.16 proceeds through this
1c mechanism,
breaking the N+≡N− bond before adding hydrogen atoms. It explains the necessity of high
N2 + H + e → N2H −3.2 1d
temperature and high-pressure reaction conditions in the H–B process. The photocatalytic
N2 + 2H + 2e → N2H2
+ − −1.10 1e
or electrocatalytic nitrogen fixation process was more in line with the association mech-
N 2 + 4H+ + 4e− → N2H4 −0.36 1f
anism by following the principle of low energy consumption, where N2 molecules were
N 2 + 5H+ + 4e− → N2H5+ −0.23 1g
hydrogenated continuously without breaking the N≡N triple bond until the first NH3
N2 +was
molecule + 6e− → 2N
6H+released. 2H3
Depending 0.55
on the hydrogenation mode, the association 1h mechanism
N + 8H + + 8e − → 2N2H4 0.27 1i
was further divided into two types: the distal binding mechanism and the alternate
2 binding
mechanism. In the distal binding mechanism, protonation occurs preferentially on the
The atoms
nitrogen exact mechanism
far from the of the nitrogen
catalyst surfacereduction reaction
without direct was ambiguous.
interaction Currently,
with the catalyst and
there are three the
after releasing recognized
first NHcatalytic
3 molecule. hydrogenation
The remaining mechanisms: dissociation
adsorbed nitrogen atoms mechanism,
continued
association
hydrogenating mechanism
until theand enzyme
second NH3catalytic
molecule mechanism
was produced.(FigureIn 2)
the[18]. The dissociation
alternating binding
mechanism
mechanism,refersthe two to nitrogen
the directatoms breaking
wereofconverted
the chemical
to NH bond
3 byin the N
accepting2 molecule
protons and the
in turn,
formation of two isolated
and the synthesized nitrogen was
NH3 molecule atoms on the catalyst
desorbed from thesurface,
catalyst which
surfacethen by aundergoes
final N–N
hydrogenation to produce NH
break. The enzyme-catalyzed 3. The H-Bapplies
mechanism processtoproceeds through
hydrogenation this mechanism,
reactions occurring
with nitrogen-fixing
breaking the N≡N bond enzymes before and other hydrogen
adding catalysts, in whichIt both
atoms. N atoms
explains are boundoftohigh
the necessity the
nitrogen-fixing
temperature and enzyme or catalyst,
high-pressure and hydrogenation
reaction conditions in the coincides [19–21].
H−B process. The Inphotocatalytic
summary, the
photocatalytic
or electrocatalytic nitrogen
nitrogen reaction
fixation was summarized
process was more as three
in linesteps: (1) N
with the 2 molecules
association were
mecha-
adsorbed
nism on the reaction
by following the principlesites ofofthelow catalyst;
energy (2) electrons and
consumption, protons
where were obtained
N2 molecules were
through a proton–coupled electron transfer process, and the
hydrogenated continuously without breaking the N≡N triple bond until the first NH3 mol-N ≡ N bond was broken to
produce NH ;
ecule was released.
3 (3) NH molecules
Depending
3 were desorbed from the catalyst surface.
on the hydrogenation mode, the association mechanism Understanding
the binding
was mode ofinto
further divided N2 two molecules on distal
types: the the photocatalyst was essential
binding mechanism and the foralternate
studying the
bind-
reaction
ing mechanism
mechanism. In the ofdistal
nitrogen reduction.
binding mechanism, protonation occurs preferentially on the
 summary, the photocatalytic nitrogen reaction was summarized as three steps: (1) N2 mol-
ecules were adsorbed on the reaction sites of the catalyst; (2) electrons and protons were
obtained through a proton−coupled electron transfer process, and the N≡N bond was bro-
ken to produce NH3; (3) NH3 molecules were desorbed from the catalyst surface. Under-
Molecules 2023, 28, 2666 standing the binding mode of N2 molecules on the photocatalyst was essential for 4 of 18
study-
ing the reaction mechanism of nitrogen reduction.

Figure 2. The
Figure 2. Themechanism
mechanismofofnitrogen fixation(a)
nitrogen fixation (a)dissociative,
dissociative,(b)(b) distal
distal associative,
associative, (c) alternative
(c) alternative
associative, (d)(d)
associative, enzymatic.
enzymatic.

3. Challenges of NRR
3. Challenges of NRR
Due to the inert nature of N2 molecules and the inherent defects of non-homogeneous
Due tosystems,
reaction the inertthe
nature of N2 molecules
development and designandofthe inherent
efficient defects
nitrogen of non-homogeneous
fixation systems face
reaction
multiple difficulties and challenges, mainly including the low visible lightfixation
systems, the development and design of efficient nitrogen systems
utilization capac- face
multiple difficulties and
ity of photocatalytic challenges,
materials, mainly including
easy compounding the low visible
of photogenerated lightchallenges
carriers, utilization ca-
pacity ofactivation
in the photocatalytic materials,and
of N2 adsorption easy compounding
competition of photogenerated
for hydrogen carriers,
precipitation during thechal-
catalytic reaction. Similarly, electrocatalysis also faces many challenges.
lenges in the activation of N2 adsorption and competition for hydrogen precipitation dur-
ing the catalytic reaction. Similarly, electrocatalysis also faces many challenges.
3.1. Low Utilization of Light Energy

3.1. LowTuning the bandgap

Utilization of Lightof semiconductor photocatalysts to accept visible light excitation
Energy
and meet the reduction potential for converting nitrogen to ammonia was necessary for
Tuning the bandgap
photocatalytic reactions.ofAsemiconductor
narrow band gap photocatalysts
was beneficialtotoaccept
improvevisible light excitation
the efficiency of
andsunlight
meet the reduction
utilization, potential
while for converting
a too-narrow band gap nitrogen to energy
reduced the ammonia levelwas necessary for
of photogen-
photocatalytic reactions.
erated electrons, resultingA narrow band gap
in an insufficient was beneficial
reduction capacitytotoimprove thereactants.
activate the efficiency of
For photocatalytic
sunlight nitrogen
utilization, while fixation, theband
a too-narrow catalyst
gapCB positionthe
reduced must be above
energy level the nitro-
of photogen-
gen reduction overpotential ( − 0.092 V vs. NHE); the ideal band gap value
erated electrons, resulting in an insufficient reduction capacity to activate the reactants.was about
For2.0 eV, corresponding
photocatalytic to a light
nitrogen absorption
fixation, range up
the catalyst to position
CB 620 nm. However,
must be the band
above gap
the of
nitrogen
semiconductor materials (Figure 3) [22] was often beyond the ideal range. For example,
reduction overpotential (−0.092 V vs. NHE); the ideal band gap value was about 2.0 eV,
conventional TiO2 had a band gap value of about 3.2 eV, making it difficult to activate in
visible light to generate photogenerated electrons.
Quantum efficiency was an important parameter describing photoelectric conversion
in photocatalysis technology. It refers to the ratio of the average number of photoelectrons
produced in a specific wavelength per unit of time to the number of incident photons. The
quantum efficiency of the catalysts developed in recent years was usually lower than 5%,
which is still a low level [23–26].
 corresponding to a light absorption range up to 620 nm. However, the band gap of semi-
conductor materials (Figure 3) [22] was often beyond the ideal range. For example, con-
Molecules 2023, 28, 2666 5 ofin18
ventional TiO2 had a band gap value of about 3.2 eV, making it difficult to activate
visible light to generate photogenerated electrons.

−2.0
−1.0
0
1.0
2.0
3.0
4.0

Band–edgepositions
Figure3.3.Band−edge
Figure positionsfor
forconventional
conventionalsemiconductors
semiconductors(vs.
(vs.NHE
NHEatatpH
pH==0).0).

3.2. Low Separation Rate of Photogenerated Carriers

Quantum efficiency was an important parameter describing photoelectric conversion
According to
in photocatalysis the principle
technology. of photocatalytic
It refers to the ratio ofnitrogen
the averagefixation,
numberthe nitrogen reduction
of photoelectrons
reaction occurs on the premise that photogenerated electrons
produced in a specific wavelength per unit of time to the number of incident photons. are separated from holesThe
and
migrate to the catalyst surface. While the migration speed of photogenerated carriers is
quantum−efficiency of the catalysts developed in recent years was usually lower than 5%,
slow (10 8 ~10−3 s) and the compounding process was relatively fast (10−9 s), the significant
which is still a low level [23–26].
speed difference leads to the photogenerated electrons and holes being extremely easy to
compound. It reduces the catalytic reaction efficiency [27]. Therefore, promoting the sepa-
3.2. Low Separation Rate of Photogenerated Carriers
ration and transfer of photogenerated electron–hole pairs and suppressing photogenerated
According
carrier to the principle
complexation of photocatalytic
in photocatalytic reactions nitrogen fixation, the nitrogen reduction
is difficult.
reaction How to suppress the migration of photogenerated carriersare
occurs on the premise that photogenerated electrons andseparated
reduce the from holes
complexa-
and
tionmigrate to the catalyst
of electron–hole pairssurface.
is the focusWhile the current
of the migration speed on
research of photogenerated carriers
photocatalysis [28,29].
is slow (10−8~10−3 s) and the compounding process was relatively fast (10−9 s), the signifi-
cant
3.3. speed difference
N2 Adsorption andleads to theDifficulties
Activation photogenerated electrons and holes being extremely
easy to compound. It reduces the catalytic
N2 , as an inert molecule, has a robust N reaction
≡N bond efficiency
energy (941[27]. kJTherefore,
·mol−1 ) and promoting
a dissoci-
the separation and transfer of photogenerated
− 1 electron−hole pairs
ation energy of up to 410 kJ·mol for the first chemical bond, which hinders its cleavage and suppressing pho-
togenerated carrier complexation
and hydrogenation. According tointhe photocatalytic
front-line orbitalreactions
theory, is the
difficult.
energy gap between the
HOMO How(σto g
suppress
2p bonding the migration
orbital) and of
LUMO photogenerated
(πg*2p carriers
antibonding and reduce
orbital) of the theN2complex-
molecule
ation
is 10.82 eV, which inhibits the injection process of electrons into the antibonding[28,29].
of electron–hole pairs is the focus of the current research on photocatalysis orbital
and hinders the activation of the N2 molecule [30]. In the multiphase catalytic process,
3.3. N2 Adsorption
reactant adsorption and onActivation Difficulties
the catalyst surface was a prerequisite for the reaction to occur,
andNthe specific
2, as an inert surface
molecule,areahasof the catalyst
a robust N≡Naffects
bondthe contact
energy between
(941 kJ·mol−1reactants and the
) and a dissoci-
exposure
ation energy ofofactive
up tosites.
410 kJ·The
molformation of chemical
−1 for the first chemical bonds between
bond, which the surface
hinders active
its cleavage
sites and N
and hydrogenation.2 in cooperation weakens the strength of N ≡ N bonds and
According to the front-line orbital theory, the energy gap between the promotes the acti-
vation of N molecules. It was the rate-determining step
HOMO (σg2p2 bonding orbital) and LUMO (πg*2p antibonding orbital) of the N2 molecule of the photocatalytic nitrogen
isreduction
10.82 eV,reaction.
which inhibits the injection process of electrons into the antibonding orbital
The reduction
and hinders reaction
the activation ofofthenitrogen in the [30].
N2 molecule presence
In theof multiphase
a photocatalyst requires
catalytic three
process,
steps: (1)
reactant dissolution
adsorption onofthe
nitrogen
catalystinsurface
water; (2)wasdiffusion of dissolved
a prerequisite for thenitrogen
reactionintowateroccur,to
the the
and liquid surface
specific film of
surface theofcatalyst;
area and (3)
the catalyst activation
affects of nitrogen
the contact between by reactants
adsorption andonthe
the
active sites on the catalyst surface. However, the solubility
exposure of active sites. The formation of chemical bonds between the surface active sitesof nitrogen in the aqueous
phase
and N2 inreaction systemweakens
cooperation at room thetemperature
strength of and
N≡N pressure
bondsisand extremely
promotes lowthe(~1 mmol·L−of1 ),
activation
− 5 2 − 1
the expansion coefficient is small (10 cm ·s ), resulting in the rate of ammonia
Nand
2 molecules. It was the rate-determining step of the photocatalytic nitrogen reduction

reaction. being limited by the process of nitrogen dissolution and diffusion in the reaction
synthesis
system
The[31,32].
reduction reaction of nitrogen in the presence of a photocatalyst requires three
steps: (1) dissolution of nitrogen in water; (2) diffusion of dissolved nitrogen in water to
3.4. Hydrogen Analysis Competition
the liquid surface film of the catalyst; and (3) activation of nitrogen by adsorption on the
Another challenge in photocatalytic nitrogen reduction was the competition with the
hydrogen precipitation reaction (HER). Since HER involves only two-electron transfer
processes (Equation (1b)), the NRR half-reaction requires a charge transfer process of at
least six electrons (Equation (1h)). HER has a kinetic advantage. Second, the HER potential
was lower than NRR regardless of acidic or basic conditions, implying that a hydrogen pre-
Molecules 2023, 28, 2666 6 of 18

cipitation process inevitably accompanied the NRR reaction. The H2 generation leads to a
decrease in nitrogen fixation efficiency and a decrease in the selectivity of the photocatalytic
reaction [33].

3.5. Other Problems in NRR

The electrocatalysis research mainly includes the following aspects: (1) Combining
with theoretical calculations further improves the calculation method and model of NRR
to provide theoretical guidance for the design of catalysts. (2) The occurrence of HER
side reaction reduces the efficiency of the electrocatalytic synthesis of NH3 . (3) In the
process of electrocatalysis, the structure of the intermediates produced by the reaction was
complex, and the production time was short. It was difficult to characterize and capture
these intermediates by the existing experimental methods.
Research on the electrocatalytic reduction in nitrogen is vital for developing an ecolog-
ical environment and new energy. The progress in the field of NRR has confirmed that it is
possible to reduce N2 to NH3 using electrocatalysis at a normal temperature and pressure.
However, the efficiency of electrocatalysis is low; it is still in the laboratory research stage.

4. Modification Strategies for the Photo(electro)catalysts

A photo(electro)catalyst is critical in determining the catalytic reduction reaction. The
research focus of nitrogen fixation technology was the construction of efficient photo(electro)
catalysts to enhance the reaction activity. The typical photocatalysis process mainly includes
three key steps: photoexcited charge generation, photogenerated charge transfer to the cat-
alyst surface and participation in the redox reaction on the surface. Each step is a necessary
condition for a catalytic reaction, so the fundamental way to enhance the performance of
the catalyst is to improve the efficiency of each step. Various photo(electro)catalyst modifi-
cation strategies have been developed, such as morphology modulation, heterostructure
construction, vacancy introduction, element doping and cocatalyst addition.

4.1. Morphology Modulation

Generally, morphological changes could affect the nanocatalyst materials’ physical and
chemical properties. Factors such as structure, dimensionality, morphology and size of inor-
ganic nanomaterials directly impact their functional properties, thus affecting their catalytic ac-
tivity and selectivity [34,35]. Nanomaterials have unique optical, electrical, magnetic, catalytic
and mechanical properties closely related to crystal morphology and morphology. Adjusting
physical morphology has become an effective method to enhance the photo(electro)catalytic
performance by adjusting the size or structure of semiconductors. Therefore, the preparation
of controllable particle size and shape semiconductor nanomaterials and the study of their
structure and morphology effects on photo(electro)catalytic properties are of great significance
for researching and developing new efficient catalytic materials.

4.1.1. Photocatalyst
There was a constitutive relationship between nanomaterials’ size, morphological
structure, and properties. Particle size affects the band gap energy, light absorption capacity,
and average free range of photogenerated charges, resulting in size quantization, structure-
dependent crystallization and the structure-induced multiple reflection effect. According
to the order from simple to complex, the structure types of semiconductor materials can
be divided into 0/2D, 1D, 3D and multi-dimensional materials [36]. The 0/2D material
refers to solid film, film or powder, which has the advantages of easy preparation and
convenient utilization. At the same time, the plane shape on the nanometer scale will
change the position of its band gap, conduction band and valence band. One-dimensional
materials, such as nanoparticles, nanowires and nanorods. It could be a semiconductor with
one-dimensional ordered geometry. Such materials often have a high specific surface area,
which can shorten the charge transfer distance and provide rich active centers and a large
light absorption area for redox reactions. Multi-dimensional materials such as 3D have more
Molecules 2023, 28, 2666 7 of 18

complex structures, which further increases the surface area of semiconductor materials,
and shows structure-induced characteristics such as multiple reflections of incident light.
For example, in recent years, 2D semiconductors have aroused great interest in pho-
tocatalysis due to their remarkable advantages [37]. One is that some 2D semiconductors
have a variable band gap through size adjustment, thus improving the light absorption
ability. At the same time, the sharp decrease in semiconductor thickness shortens the
migration distance of photogenic charge from the bulk phase to the surface phase, which is
advantageous to the separation and transportation of photogenerated charge. In addition,
for the ultrathin properties of 2D materials, the abundant reaction sites generated by a
high specific surface area will also be favorable for photocatalytic reactions. Gao et al. [38]
prepared AgCl/δ-Bi2 O3 nanosheets with a thickness of about 2.7 nm by hydrothermal
precipitation. The structural properties of the catalysts, including morphology, crystallinity,
optical properties and energy band structure, were analyzed by SEM, TEM and AFM
tests. The characterization results show that the ultrathin two-dimensional nanomaterials
have a larger specific surface area and two-dimensional anisotropy, exposing more sur-
face unsaturated paired atoms, increasing the active surface centers and shortening the
charge migration distance to achieve effective separation of electron–hole pairs. Meanwhile,
surface atoms tend to escape from the lattice during the size reduction in nanomaterials,
inducing surface defects. Feng et al. [39] successfully prepared surface oxygen vacancy-
modified Bi2 O2 CO3 (i.e., BOC/OV) by continuously compressing the size of nanomaterials
at room temperature. The size of the individual sheets has been reduced to 10 × 10 nm,
the crystalline periodic boundary conditions are disrupted, and the atomic density near
the surface layer of the nanoparticles is diminished. Under the synergistic effect of surface
vacancies and the small size effect, the adsorption activation of BOC/OV on N2 is en-
hanced, the complexation rate of photogenerated carriers is reduced and the photocatalytic
reduction performance is enhanced to 10 times the original BOC yield. In addition, the
hollow structure can slow the escape of nitrogen and reaction intermediates and prolong
the nitrogen residence time due to cavities while shortening the electron migration distance
and inhibiting photogenerated carrier complexation. Vu et al. [40] calcined MIL-68-In(Ru)
precursors in the air to obtain Ru-doped In2 O3 materials. The nanoparticles are relatively
uniformly distributed and self-assembled into a hollow peanut structure, which facilitates
the separation and transport of photogenerated electrons and holes and improves the
light energy utilization through multiple reflection and scattering processes of light. For
analysis and comparison, catalysts with specific morphological structures from the above
and recent studies are compiled in Table 2, and their morphological modulation methods,
photoreaction conditions and ammonia production efficiency are summarized.

Table 2. Comparison of recent photocatalysts with specific morphologies and nitrogen fixation properties.

Morphological Nitrogen Sacrificial Light

Photocatalyst Preparation Method Ammonia Yield References
Characteristics Source Agent Source
Nanospheres
Hydrothermal–
Ag/PM-CdS(e) (diameter of about N2 - λ > 420 nm 0.343 µg·h−1 ·mg−1 [41]
Etching
14.2 nm)
Nanosheets
Hydrothermal
AgCl/δ-Bi2 O3 (thickness of about N2 - λ > 420 nm 606 µmol·h−1 ·g−1 [42]
precipitation method
2.7 nm)
Micro-nanosheets Room temperature
BOC/OV3 N2 Na2 SO3 λ > 400 nm 1178 µmol·L−1 ·g−1 ·h−1 [43]
(<10 × 10 nm) reaction-reduction
Hollow peanut
Ru-In2 O3 Air Calcination N2 Methanol UV-vis 44.5 µmol·g−1 ·h−1 [40]
structure
NYF/NV- λ~980 nm 1.72 mmol·L−1 ·gcat −1 or
Nanotubes Solvothermal method N2 Ethanol [44]
CNNTs or > 420 nm 5.30 mmol·L−1 ·gcat −1
Mesoporous hollow Templating agent
Au/HCNS-NV N2 Methanol λ > 420 nm 783.4 µmol·h−1 ·gcat −1 [45]
spheres calcination-reduction
1T’- Hydrothermal
Nanocages N2 Methanol UV-vis 9.8 mmol·L−1 ·h−1 ·g−1 [46]
MoS2 /CNNC method
Low-temperature
Nv&Od-CN Porous hollow prisms hydrothermal– N2 Methanol λ > 420 nm 118.8 mg·L−1 ·h−1 ·gcat −1 [47]
calcination
Molecules 2023, 28, 2666 8 of 18

4.1.2. Electrocatalyst
For electrocatalysis, adjusting the morphology of the catalyst is also a powerful strategy
to improve the performance of NRR. Li et al. reported that porous palladium ruthenium
nanosheets (PdRu NS-NF) were grown in situ on Ni foam with Ni foam as a reducing
agent and substrate [48]. These ultrathin nanosheets have a high density of unsaturated
atoms and a high specific surface area, providing rich active sites and available channels for
charge transport. The ammonia yield and Faraday efficiency (FE) of PdRu NS-NF without
adhesive are 20.46µg·h−1 cm−1 and 2.11%, respectively, showing excellent activity and
stability in the electrocatalytic reduction in nitrogen.
In addition, low coordination sites can be formed by adjusting the size of the electrocat-
alyst, which affects the binding strength of the reaction intermediates, thus optimizing the
activity and selectivity of the electrocatalyst. Shi et al. successfully prepared sub-nanometer
(≈0.5 nm) Au clusters on TiO2 substrate and formed stable Au-O-Ti bonds through lattice
oxygen [49]. Three kinds of Au/TiO2 catalysts with different metal sizes were prepared
simultaneously for comparison. The experimental results show that due to the high surface
energy of small metal clusters, strong chemical bonds were always formed between the
coordination lattice oxygen of atomic metal and oxide to maintain the stability of the metal.
Therefore, the sub-nanometer Au clusters anchored on TiO2 have stability under long-term
electrolysis conditions, significantly improving the ammonia yield of electrocatalytic NRR
(21.4 µg·h−1 mg−1 cat ) and FE (8.11%). It is much better than the best effect of N2 fixation
under environmental conditions and even comparable to the yield activation energy at
high temperature and/or high pressure. Furthermore, the active site of the catalyst could
be improved effectively by adjusting the crystalline surface of the catalyst through good
atomic arrangement and coordination. However, there is little research on applying crystal
surface modulation to electroreducing nitrogen reactions, so further research in this area
can be conducted.

4.2. Heterostructure Construction

Heterojunctions refer to the interfacial region formed after the contact between two dif-
ferent semiconductors; the construction of heterojunctions enhances the light absorption
ability of catalysts and improves the quantum efficiency with the help of the window
effect, and can promote the separation of photogenerated electrons and holes by using
the interfacial impact [50,51]. Generally, the heterojunctions formed between different
semiconductors were classified into three types of conventional heterojunctions (including
type-I, type-II and type-III), p-n heterojunctions and Z-scheme heterojunctions (including
conventional Z-scheme, all-solid Z-scheme and direct Z-scheme).
Fan et al. [52] used a precipitation method to grow In(OH)3 nanoparticles on g–C3 N4
nanosheets to synthesize 0D/2D type-I heterojunctions (Figure 4a). Although In(OH)3
in the heterojunction cannot produce photogenerated electrons in visible light, its defect
energy level was close to the CB of g–C3 N4 , which enables it to trap excited-state electrons
of g–C3 N4 , improving the separation efficiency of electron–hole pairs, extend the lifetime
of photogenerated carriers, and obtain excellent nitrogen fixation activity and stability.
Mou et al. [53] used terephthalic acid as a molecular probe. The synthesized g–C3 N4 /ZrO2
was verified to be a type-II heterojunction by capturing the hydroxyl group by fluorescence
(Figure 4b). Among them, g–C3 N4 has excellent light absorption ability and can be used
for light trapping. The photogenerated electrons migrate from the CB of g–C3 N4 to the
CB of ZrO2 because of the type-II heterojunction. It promotes the reverse movement of
photogenerated electrons and holes, reducing the complexation rate of photogenerated
carriers. P-n type has a similar structure to the type-II heterojunction, and in p-n-type
photocatalysts, the CB and VB energy levels of p-type semiconductors are usually higher
than those of n-type semiconductors. Due to the internal electric field and energy band, the
p-n heterojunction has a faster charge separation rate than the type-II heterojunction due
to the synergistic effect of the internal electric field and energy band alignment [54]. The
NiS/KNbO3 prepared by Zhang’s research group [55] has a strong N2 reduction ability
Molecules 2023, 28, 2666 9 of 18

under simulated solar irradiation. Since the Fermi energy level of KNbO3 was higher
than that of NiS, electrons spontaneously migrate from KNbO3 to NiS, which causes the
energy band potential of NiS to increase and the composite material to constitute a p-n
heterojunction and generate an internal electric field. Driven by the energy band structure
and the built-in electric field, electrons in NiS were transferred to the CB of KNbO3 , while
holes in KNbO3 were transferred to the VB of NiS, and the photogenerated electrons and
holes achieved efficient spatial separation (Figure 4c). Thus, NiS/KNbO3 exhibited good
photocatalytic efficiency in N2 reduction, which was 1.9 and 6.8 times higher than that of
KNbO3 and NiS, respectively. Inspired by artificial photosynthesis, the concept of Z-scheme
heterojunction was further proposed to improve the photocatalytic system’s redox potential.
Duan et al. [56] synthesized three-dimensional Cu2 O/MoS2 /ZnO nanocomposites with
copper mesh as a substrate for photocatalytic N2 reduction experiments under visible light.
Excellent interfacial contact achieved a high ammonia yield, which was 4.24 and 2.58 times
higher than ZnO and Cu2 O. Characterization tests showed that the photogenerated charges
in the composite showed a double Z-scheme transport path, the weak oxidation holes
and weak reduction electrons in the charge transfer process were directly quenched and
the photogenerated carrier separation efficiency and catalyst reduction capacity were
Molecules 2023, 28, x FOR PEER REVIEW 10 of 19
significantly enhanced. At the same time, a broad spectral response and high stability were
achieved (Figure 4d).

−2.0

−1.0
Potential (V vs. NHE)

0.0

1.0

2.0

3.0

4.0

−2.0 −2.0

−1.0 −1.0
Potential (V vs. NHE)

Potential (V vs. NHE)

0.0 0.0

1.0 1.0

2.0
2.0
3.0
3.0
4.0
4.0

Figure 4.4. Schematic

Schematic illustrations
illustrations of ofphotocatalytic
photocatalyticNN2 2fixation
fixationover
over(a)
(a)OV-In(OH)3 /g–C
OV-In(OH) 3/g−C33N4, (b) g–
g-
C33N44/ZrO
/ZrO2,2(c)
, (c)NiS/KNbO
NiS/KNbO ,
3, (d)
3 (d)
Cu Cu
2 O/MoS
O/MoS
2 2 /ZnO–cm.
/ZnO−cm.
2

At
At present,
present,heterojunction
heterojunctionelectrocatalysts areare
electrocatalysts mainly
mainlyconcentrated
concentratedon type-II catalysts.
on type-II cata-
Hu
lysts. Hu et al. [57] have proven that compared with g−C3N4 or ternary metal sulfide, the
et al. [57] have proven that compared with g–C 3 N 4 or ternary metal sulfide, the
construction
construction of ofg–C
g-−C3N
3N4 4with
withternary
ternarymetal
metalsulfide could
sulfide couldsignificantly improve
significantly improvethethe
nitrogen
nitro-
fixation efficiency.
gen fixation WhenWhen
efficiency. the mass
the fraction of ZnMoCdS
mass fraction was 80%,
of ZnMoCdS wasthe heterojunction
80%, system
the heterojunction
had the highest nitrogen fixation capacity. A large number of sulfur vacancies
system had the highest nitrogen fixation capacity. A large number of sulfur vacancies acted as
active
acted ascenters
activeand significantly
centers improvedimproved
and significantly electrocatalytic activity. activity.
electrocatalytic
4.3. Introduction of Vacancies
4.3. Introduction of Vacancies
Defect engineering was an effective strategy to modulate materials’ electronic and
Defect engineering was an effective strategy to modulate materials’ electronic and
chemical structure. Defects were mainly classified into four categories based on size: point
chemical structure. Defects were mainly classified into four categories based on size: point
defects, line defects, surface defects and bulk defects. Among them, point defects were
defects, line defects, surface defects and bulk defects. Among them, point defects were a
a type of defect that deviates from the crystal structure or normal arrangement in the
type of defect that deviates from the crystal structure or normal arrangement in the lattice
lattice nodes or adjacent microscopic regions, which were mainly classified into oxygen
nodes or adjacent microscopic regions, which were mainly classified into oxygen vacan-
cies (OV), sulfur vacancies (SV) and nitrogen vacancies (NV) according to elemental cate-
gories [58]. Whether in photocatalysts or electrocatalysts, how to introduce oxygen vacan-
cies (OVs)—which are anionic vacancies with a low free-energy formation and are usually
easily formed in transition metal oxides—is the topic that is most studied. The created
Molecules 2023, 28, 2666 10 of 18

vacancies (OV), sulfur vacancies (SV) and nitrogen vacancies (NV) according to elemental
categories [58]. Whether in photocatalysts or electrocatalysts, how to introduce oxygen
vacancies (OVs)—which are anionic vacancies with a low free-energy formation and are
usually easily formed in transition metal oxides—is the topic that is most studied. The
created oxygen vacancies can be used as active sites for adsorption reactants and reaction
intermediates, lowering the activation energy barrier and promoting electrochemical re-
actions. In addition, the introduction of vacancies can affect the electronic structure of
catalysts and enhance charge. In addition, the introduction of vacancies can affect the
electronic structure of the catalyst, enhance charge transfer and expose more metal sites
with unsaturated coordination.

4.3.1. Photocatalyst
The modification effect of introducing vacancies in materials was generally reflected in
three aspects: (1) the generated vacancies could act as trapping centers for photogenerated
electrons or holes and inhibit photogenerated charge complexes; (2) they act as active
centers and promote the adsorption and activation of reactant molecules; and (3) they11adjust
Molecules 2023, 28, x FOR PEER REVIEW of 19
the band gap energy of catalysts and enhance the light absorption capacity. Cao et al. [59]
used metal doping such as Ni or Mo to induce distortion in the lattice of CdS, resulting in
vacancy defects on the material surface, and performed photocatalytic nitrogen reduction
reduction
tests. There tests.
was There was a positive
a positive correlation
correlation between between the sulfur
the sulfur vacancy
vacancy concentration
concentration and
and ammonia generation rate within a certain reaction time, where Mo 0.1Ni0.1Cd0.8S con-
ammonia generation rate within a certain reaction time, where Mo0.1 Ni0.1 Cd0.8 S contained
tained
the the highest
highest sulfur sulfur
vacancyvacancy concentration,
concentration, and itsand its ammonia
ammonia yieldyield was correspond-
was correspondingly
ingly the highest (Figure 5a). Combined with the analysis of ICP,
the highest (Figure 5a). Combined with the analysis of ICP, TPD, and nitrogen TPD, and nitrogen fixa-
fixation
tion reaction results, the surface sulfur vacancies could not only serve as active
reaction results, the surface sulfur vacancies could not only serve as active sites for the sites for
the adsorption
adsorption and activation
and activation of N2of N2 molecules,
molecules, but also
but could couldpromote
also promote the interfacial
the interfacial charge
charge transfer
transfer from thefrom the to
catalyst catalyst
the N2tomolecules,
the N2 molecules, thus significantly
thus significantly improving improving the
the nitrogen
nitrogen
photo photocapacity.
fixation fixation capacity.

Figure 5.
Figure 5. The
The optimized
optimizedgeometry
geometryofofthe
theoptimal
optimalNN2 adsorption models on (a) bulk SCN and (b)
2 adsorption models on (a) bulk SCN and
SCNNSs−550. Reprinted with permission from Ref. [59]. Copyright
(b) SCNNSs–550. Reprinted with permission from Ref. [59]. Copyright2018, Elsevier.
2018, Elsevier.

In addition,
In addition,thetheability
abilityofof nitrogen
nitrogen vacancies
vacancies to selectively
to selectively use nitrogen
use nitrogen as an as an ad-
adsorbed
species due to matching
sorbed species the shape
due to matching the and
shapesize
andofsize
nitrogen atomsatoms
of nitrogen implies that the
implies thatphotocat-
the pho-
alytic reaction
tocatalytic can directly
reaction utilize
can directly air asair
utilize a nitrogen source
as a nitrogen and reduce
source the production
and reduce cost.
the production
Dong et al. [60] first reported that nitrogen vacancies enable
cost. Dong et al. [60] first reported that nitrogen vacancies enable g–C N to selectively adsorb
3 4 g−C3N4 to selectively
and
adsorbreduce N2 in gas
and reduce N2 inmixtures without
gas mixtures interference
without from from
interference otherother
gases. By the
gases. density
By the den-
flooding theory
sity flooding (DFT)
theory calculations,
(DFT) N2 molecules
calculations, tendtend
N2 molecules to adsorb on nitrogen
to adsorb vacancies
on nitrogen and
vacancies
form σ-bonds
and form with two
σ-bonds withadjacent C atoms.CThe
two adjacent coupling
atoms. The mode of Nmode
coupling 2 molecules
of N2 changes as
molecules
changes as the nitrogen–nitrogen bond length is extended from 1.117 Å to 1.214 Å , thus
demonstrating that the nitrogen vacancies activate N2. In addition to the work on nitrogen
vacancies, a recent research team introduced carbon vacancies on the surface of g−C3N4
(SCNNSs) catalysts using sulfur doping and synthesized nanosheets with a graded pore
Molecules 2023, 28, 2666 11 of 18

the nitrogen–nitrogen bond length is extended from 1.117 Å to 1.214 Å, thus demonstrating
that the nitrogen vacancies activate N2 . In addition to the work on nitrogen vacancies,
a recent research team introduced carbon vacancies on the surface of g–C3 N4 (SCNNSs)
catalysts using sulfur doping and synthesized nanosheets with a graded pore structure
and high specific surface area [61]. DFT simulated the adsorption configuration of N2
on SCNNSs–550, and the optimization results showed that the carbon vacancies more
easily adsorbed N2 molecules in SCNNSs–550 with a calculated adsorption energy of
−0.665 eV, which is 1.99 times higher than that of bulk SCN. The charge density difference
of the molecules (Figure 5b) showed that the charge separation efficiency was increased
by transferring photogenerated electrons from the carbon vacancies in SCNNSs–550 to N2
molecules. In contrast, N2 molecules were activated to form high-energy intermediates
(–N2 H or HN = NH) to promote the photocatalytic nitrogen fixation reaction.

4.3.2. Electrocatalyst
Based on DFT theoretical calculations, Yao et al. [62] proposed a strategy to optimize
the NRR performance of BiVO4 catalysts by regulating the oxygen vacancy concentration.
They successfully prepared efficient BiVO4 catalysts containing different OVs concentra-
tions by a simple hydrothermal method with reasonable pH adjustment. The highest
concentration of oxygen vacancies was obtained at pH = 7, and the best nitrogen reduction
performance was achieved. The ammonia synthesis rate was 8.6 µg·h−1 ·mg−1 cat at −0.5 V
vs. RHE potential with a Faraday efficiency of 10.04%. It was confirmed that oxygen vacan-
cies play an essential role in nitrogen reduction. The introduction of oxygen vacancies in
the electrocatalyst can enhance the adsorption of N2 adsorption and optimize NRR activity.
Researchers could take advantage of the present experience in the construction of oxygen
vacancies that has been reported in order to develop more efficient oxygen-containing
vacancy catalysts, thus promoting the development of this new field of NRR.
Oxygen and sulfur are located in the same main group and have similar chemical
properties. The researchers speculated that the sulfur vacancies (SVs), similar to OVs,
could influence the catalysts’ energy band structure and electronic structure and act as
N2 adsorption sites to induce N2 activation, thus affecting their electrocatalytic NRR
performance [63].
Similar to photocatalysis, the introduction of nitrogen heteroatoms in electrocatalysis
is required to create a net positive charge on the adjacent carbon atoms, thus facilitating the
adsorption and activation of N2 on the catalyst. The experimental results showed that the
NH3 yield was 8.09 µg·mgcat.−1 ·h−1 with a Faraday efficiency of 11.59%, which was about
10 times higher than that of the catalyst without nitrogen vacancies [64].
Due to the stable structure of N2 itself, it is weakly combined with heterogeneous
catalysts. It hinders the development of photocatalytic nitrogen fixation, which requires
changing the structure of the catalyst to activate the N atom. Vacancies (oxygen vacancies,
sulfur vacancies, nitrogen vacancies) could effectively modulate the catalyst’s electronic
structure and band gap and optimize the charge distribution of the catalyst. In addition,
vacancies could adsorb and activate inert N2 molecules, lowering the reaction barriers and
improving photocatalytic efficiency [65–72].

4.4. Cocatalyst Addition

Cocatalyst was a conductor (or semiconductor) coupled with a semiconductor to
improve the overall catalytic activity, which improves the performance of photocatalysts
in three main ways: (1) reducing the activation energy or overpotential of redox half-
reactions; (2) promoting electron–hole pair separation and inhibiting photogenerated charge
complexes; (3) inhibiting photocorrosion and improving the stability of photocatalytic
materials. The two commonly used cocatalysts in the nitrogen fixation reaction system
were reduced and plasma cocatalysts [73–77].
MXene has excellent electrical, optical and thermodynamic properties. It was expected
to replace noble metal cocatalysts as a new, reduced cocatalyst. Liao et al. [78] used 2D–
 Molecules 2023, 28, x FOR PEER REVIEW 13 of 19
Molecules 2023, 28, 2666 12 of 18

Gold nanoparticles (Au NP) produce a localized surface plasmon (LSPR) effect when
used as a cocatalyst. Under visible light irradiation, gold nanoparticles deposited on the
layered Ti3 C2 MXenes as a cocatalyst for P25, and the ammonia yield of the optimized 6%
surface of the semiconductor induce the production of high−energy electrons (hot elec-
Ti3 C2 MXenes–P25 sample under full-spectrum irradiation was 10.74 µmol·g−1 ·h−1 , which
trons). These electrons can overcome the Schottky barrier and are irreversibly injected into
wasthefive times higher than
semiconductor’s that of band.
conduction pure P25. The experimental
The photogenerated tests and
electrons andDFTholesresults
are spa- showed
thattially
Ti3 Cseparated
2 MXenes played an essential role in photogenerated electron–hole
in the semiconductor and metal nanoparticles, thus inhibiting photogen- separation
anderated
N2 adsorption activationNazemi
charge complexation. by storing electrons
and EI-Sayed from
[80] usedthe excited-state
hollow Au-Ag2O P25 (Figure 6a).
nanocages
Secondly, Ti C MXenes can facilitate the reaction between
to convert3 N22 to NH3 in a pure water system with an average ammonia yield adsorbed N 2 and of the
28.2stored
photoelectrons
mg·m ·h and
−2 −1 and are proven
an apparent to have
quantum an effective
efficiency cocatalyst.
of 1.2% Carbonsunlight
under simulated quantum dots have
irradia-
tion (the
attracted light source
much wasas
attention monochromatic
a new class of light at 685nanomaterials
carbon nm). Au generates not only
because of hot
theirholes
low cost,
lowand electrons
toxicity, through
chemical LSPR excitation,
inertness, superiorwhich
waterprovides theeasy
solubility, active center of water oxida-
functionalization and simple
tion androutes.
synthesis nitrogenWang
reduction,
et al.but also
[79] collects photogenerated
developed a composite electrons
system of from Ag2O, inhib-
biological nitrogen–
its the electron–hole complexation, improves the charge transfer
fixing bacteria modified by carbon quantum dots (CDs). CDs have the properties efficiency of NRRof and
electron
significantly enhances the photocatalytic NRR activity (Figure 6c). In addition to Au na-
donors and acceptors. Their binding to nitrogen-fixing enzymes changed the α–helix of
noparticles, other metal-based materials such as Ag, Cu and Ru can also achieve the LSPR
nitrogen-fixing enzymes’ structure, accelerating the electron transfer in the catalytic process
effect. Mao et al. [81] developed a photothermal catalytic system using multifunctional Ru
andnanoparticles
significantlyasincreasing the nitrogen-fixing
plasma-assisted enzyme activity
catalysts and adsorption (Figure
activation 6b).NThe
sites for excellent
2 mole-
light capture
cules. TiO2-xability
Hx hasand unique
abundant OVsphotogenerated
that increase the electron
electrontransfer
densityability
aroundofRu carbon
nanopar- quantum
dots proved
ticles. Based toon
bethe
a potentially
LSPR-induced reduced
binding cocatalyst
energy, Hwith promising
donation applications
and feedback between inthe
the field
of photocatalytic
TiO2-xHx surfacenitrogen
and the Rufixation.
catalyst could be achieved.

Figure
Figure 6. (a)
6. (a) Schematic
Schematic illustrationfor
illustration forthe
thepromotion
promotion effect
effect of
ofTi
Ti33CC2 2MXenes
MXenesononP25 forfor
P25 photocata-
photocatalytic
lytic NRR, reprinted with permission from Ref. [78]. Copyright 2020, Elsevier. (b) Schematic dia-
NRR, reprinted with permission from Ref. [78]. Copyright 2020, Elsevier. (b) Schematic diagram of
gram of electron transfer pathways for nitrogenase/CD hybrids, reprinted with permission from
electron transfer
Ref. [22]. pathways
Copyright for Wiley
2019, John nitrogenase/CD
and Sons (c) hybrids,
Electronicreprinted withofpermission
band structure the Ag2O and from
Ag2O- Ref. [22].
Copyright 2019, John Wiley and Sons (c) Electronic band structure of
Au photocatalyst for the nitrogen reduction reaction, reprinted with permission from the Ag 2 O and Ag 2 Cop- photo-
O-Au
Ref. [80].
yright 2019, Elsevier (d) Schematic illustration of solar thermal ammonia synthesis
catalyst for the nitrogen reduction reaction, reprinted with permission from Ref. [80]. Copyright on Ru/TiO 2-xHx. 2019,
Reprinted with permission from Ref. [81]. Copyright 2018, Elsevier.
Elsevier (d) Schematic illustration of solar thermal ammonia synthesis on Ru/TiO2-x Hx . Reprinted
with permission from Ref. [81]. Copyright 2018, Elsevier.

Gold nanoparticles (Au NP) produce a localized surface plasmon (LSPR) effect when
used as a cocatalyst. Under visible light irradiation, gold nanoparticles deposited on the
surface of the semiconductor induce the production of high–energy electrons (hot electrons).
These electrons can overcome the Schottky barrier and are irreversibly injected into the
Molecules 2023, 28, 2666 13 of 18

semiconductor’s conduction band. The photogenerated electrons and holes are spatially
separated in the semiconductor and metal nanoparticles, thus inhibiting photogenerated
charge complexation. Nazemi and EI-Sayed [80] used hollow Au-Ag2 O nanocages to con-
vert N2 to NH3 in a pure water system with an average ammonia yield of 28.2 mg·m−2 ·h−1
and an apparent quantum efficiency of 1.2% under simulated sunlight irradiation (the light
source was monochromatic light at 685 nm). Au generates not only hot holes and electrons
through LSPR excitation, which provides the active center of water oxidation and nitrogen
reduction, but also collects photogenerated electrons from Ag2 O, inhibits the electron–hole
complexation, improves the charge transfer efficiency of NRR and significantly enhances the
photocatalytic NRR activity (Figure 6c). In addition to Au nanoparticles, other metal-based
materials such as Ag, Cu and Ru can also achieve the LSPR effect. Mao et al. [81] developed
a photothermal catalytic system using multifunctional Ru nanoparticles as plasma-assisted
catalysts and adsorption activation sites for N2 molecules. TiO2-x Hx has abundant OVs that
increase the electron density around Ru nanoparticles. Based on the LSPR-induced binding
energy, H donation and feedback between the TiO2-x Hx surface and the Ru catalyst could
be achieved. Therefore, ammonia could be synthesized on the Ru surface by an acceptor
mechanism (Figure 6d, Mechanism I) and generated by a reaction between Ru-activated
N and Hinc on the TiO2-x Hx surface (Figure 6d, Mechanism II). This reaction mechanism
prevents the poisoning of the Ru surface by H during thermal synthesis and ensures the
high efficiency and stability of nitrogen fixation [26,82–86].
Oshikiri et al. [87] doped the strontium titanate photoelectrode with Au NPs deposited
on the surface by niobium immersed in the anode with ethanol as a sacrificial donor. A
Ru-based cocatalyst was used to modify Nb–SrTiO3 with an N2 –saturated aqueous HCl
solution. The spacer of this photoelectrochemical system effectively prevented the further
oxidation of ammonia to nitrate during the catalytic process. In addition, the potential
chemical difference was generated by the different pH values of the cathode and anode
chambers, thus accelerating the rate of NH3 synthesis.
Liu et al. [88] synthesized Co element-doped sulfur vacancy-rich MoS by introducing
sulfur vacancies at the MoS basal position and using doped Co elements to replace Mo in
the lattice. The catalyst showed excellent NRR activity. The best Faraday efficiency was
10%, with an ammonia yield of 0.63 mmol·h−1 ·g−1 . It was attributed to the fact that the Co
element doping accelerated the adsorption and dissociation of N2 on the defective MoS,
promoting the NRR process.

4.5. Computational Modeling

The current computational modeling of photocatalytic and electrocatalytic reactions
was mainly based on the density function theory (DFT) calculations. Gao et al. [89] used
DFT calculations to load single atoms Pd and Pt onto g–C3 N4 , respectively. It signifi-
cantly reduced the reaction potential and enhanced the photocatalytic reduction in CO2 to
HCOOH and CH4 . Chu et al. [90] delved into the role of Mo doping in MnO2 catalysts and
further evaluated the rationality of the distal binding mechanism by DFT calculations. Con-
cerning the reported theoretical study and the fact that N2 H4 was not found in the reaction
products, a possible distal binding mechanism of Mo3 /Fe2 @ZC–cm photocatalyst during
hydrogenation was proposed. In the nitrogen reduction reaction, the photocatalyst pro-
vides abundant photogenerated electrons, water provides protons (H+ ), and the metal sites
near the oxygen vacancies could act as active centers to adsorb and activate N2 molecules
but also facilitate the charge transfer from the photocatalyst to the N2 molecules. In this
environment, the Mo/Fe factor adsorption activates the distal N atom in the N2 molecule
to bind to H+ , weakening the stable N≡N triple bond. The NH3 molecule was formed and
successfully desorbed in the subsequent proton-coupled electron transfer process. The N
atom of the other one continued to bind to H+ until another NH3 was formed and released.
At this point, the reaction process of N2 reduction to NH3 was completed, and the next
cycle proceeded [91–95].
Molecules 2023, 28, 2666 14 of 18

5. Conclusions and Prospects

Photo(electro)catalysis uses sunlight and electricity to reduce nitrogen to ammonia
through catalysts. It provides a promising development path for achieving green and
sustainable ammonia production. This paper reviews and discusses the research progress
on photo(electro)catalytic nitrogen reduction. After years of efforts, photo(electro)catalytic
nitrogen fixation technology has made significant progress but has not yet reached the
requirement of industrial production. To promote the practical application of the technology
for nitrogen fixation, future research work prospects and the following points are proposed
in this field.
1. Formulate a unified evaluation standard for nitrogen fixation systems. Various
factors, including reaction equipment, reaction temperature and pressure, light
source and intensity, and product detection methods, influenced the stability of
photo(electro)catalytic efficiency. In addition, the evaluation standard of the pho-
tocatalytic NRR reaction is usually based on the absolute yield and evolution rate
of ammonia production (µmol·gcat −1 h−1 or µmol·h−1 ). With the innovation and
development of the photocatalytic reaction system, reactors’ design types have been
enriched [92]. The application form of photocatalyst is no longer a single suspension
type, and the supported catalyst that is convenient for recovery and utilization has
also begun to receive attention [93]. How to make a uniform and fair comparison
of the performance of these different types of photocatalysis systems has become a
thorny problem. In addition to specifying various parameters in detail in the report,
the number of substances that mainly play a catalytic role and the corresponding
active sites are discussed. Therefore, a reliable and strict evaluation standard for the
photo(electro)catalytic nitrogen fixation must be established to ensure the reliability
and comparability of the experimental data.
2. Because of the low reaction efficiency caused by the poor solubility of the N2 molecule,
it is considered that the nitrogen source used in the photo(electro)catalytic reaction can
be replaced. Nitrogen-based compounds such as nitrate, nitrite and nitrogen oxide
are readily soluble in water. Therefore, the problem of N≡N cracking and activation
could be avoided, and the hydrogen evolution reaction could be inhibited. Similarly,
water vapor can also be used as the proton source. Simplifying the traditional gas–
liquid–solid three-phase reaction into a gas–solid two-phase reaction is a potential
method to improve the efficiency of the NRR reaction.
3. Recently, a first-principle calculation combined with kinetic analysis has been widely
used to predict the reaction potential barrier of the rate-determining step. However,
the precise reaction kinetics theory has not been determined and is still developing. It
is necessary to conduct more in-depth thermodynamic and kinetic studies to under-
stand the catalytic performance of ammonia synthesis more practically. For example,
the photo(electro)catalytic nitrogen reduction process was studied at the molecular
or atomic level by combining experiments and theoretical calculations. Although
some of the studies combine theory and experiment, most theoretical calculations
focus on the free–energy change in the active intermediate—the energy barrier of the
rate-limiting step. These calculations of the adsorption energy of N2 are assumed to
be performed under vacuum conditions, ignoring the influence of the determinants of
the electrochemical system (e.g., temperature, pH, mass transfer rate, proton supply,
N2 solubility), which are different from the actual experimental conditions. Given
these problems, in-situ experimental techniques can be used to capture and identify
reaction intermediates and monitor the microscopic changes of catalysts to assist theo-
retical research. Therefore, it is necessary to further improve the calculation method
and model of NRR on the surface of non-homogeneous catalysts to combine theo-
retical calculations and experiments and to provide further guidance for designing
electrocatalyst structures.
4. Currently, the catalytic activity and selectivity of catalysts for ammonia synthesis
in aqueous solutions are extremely low. One of the main factors is the presence of
Molecules 2023, 28, 2666 15 of 18

competition from side reactions. Therefore, the catalytic activity and selectivity can be
significantly improved by suppressing the occurrence of side reactions. Specifically,
optimizing the size and morphology of catalysts can generate favorable coordination
sites, influence the binding strength of reactants or key intermediates on the catalyst
surface and construct defect engineering of catalysts. It was necessary to capture
photoelectrons and sub-stable electrons through vacancies and transfer them into the
antibonding orbitals of adsorbed N2 to promote the breakage of N≡N bonds. The
construction of stress engineering to regulate the atomic surface spacing and bond
length also can change the catalyst’s electronic structure, thus facilitating the nitrogen
reduction reaction. In addition, while exploring effective catalysts and constructing
excellent photocatalytic systems for future research, we should also pay attention to
the efficiency and stability issues.

Author Contributions: Methodology, Q.S.; Project Administration, Q.S.; Writing–Original Draft

Preparation, C.Z.; Writing–Review and Editing, C.Z. and Q.S.; Validation, C.Z. and Q.S. All authors
have read and agreed to the published version of the manuscript.
Funding: Financial support for carrying out this work was provided by the Doctoral Research
Foundation of Weifang University (2022BS13).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

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