1. Introduction
The annual increase in carbon dioxide (CO
2), one of the contributors to global warming, poses a serious threat to human survival and development [
1]. Achieving carbon neutrality or net-zero CO
2 emissions is therefore critical for ensuring the sustainable development of human society [
2]. To reduce CO
2 emissions, alternative methods should be developed to replace the fossil-fuel-intensive industries, such as heating supply, transportation tools, and chemical manufacturing. Benefiting from renewable energy technology, clean electricity-driven chemical synthesis with abundant feedstocks is one of the promising eco-friendly processes for the plausible eventual innovation of synthetic chemistry [
3]. The mild operation conditions, aqueous circumstance adaptation, and device miniaturization and modularization, generally make them more sustainable and convenient replacements for fossil-fuel technologies that require high temperatures and pressures [
4].
Among the modern technologies of electrosynthesis, catalytic reduction of CO
2 (CO
2RR) has been claimed to be one of the effective decarbonization strategies [
5]. By achieving carbon neutrality or even negative emissions, the CO
2RR has been continuously investigated for its potential to efficiently convert CO
2 into valuable compounds, especially low-carbon fuels, such as alcohols and hydrocarbons [
6]. With the prospective development of nanomaterial science, high selectivity of specific products can be achieved with superior efficiency by the accurate construction and precise modification of the heterogeneous catalysts loaded on electrodes [
7]. However, it is still challenging to further introduce CO
2 molecules into value-added transformation processes with a broad scope of products, such as long carbon chains or heteroatom-containing molecules. The electrocatalytic CO
2 reduction process should thus incorporate bond-forming events involving atoms other than C, H, and O [
8]. The incorporation of nitrogen atoms can lead to the generation of nitrogenous organic compounds, including urea, amines, amides, and amino acids. These substances are particularly valuable owing to their versatile applications in fields such as synthetic chemistry, pharmaceutical research, agricultural science, and aerospace engineering. Integrated nitrogen fixation for CO
2 conversion extends the feasible application of electrosynthesis and provides a new way for CO
2 resource utilization.
Currently, the practical syntheses of these
N-containing small molecules are dependent on energy-intensive technologies. Urea is thermochemically synthesized by coupling NH
3 and CO
2 at 210 bar and 200 °C, a process known as the Bosch-Meiser urea process. Amines are generated by the amination of alcohols with NH
3 at 100–250 °C and 50–250 bar. Meanwhile, the NH
3 required for these reactions is produced via the Haber-Bosch process, which operates under conditions of 400–500 °C and 100 bar pressure [
9]. Although H
2 can be produced through electrochemical water splitting for the Haber-Bosch reaction, these inseparable, multi-step synthetic industries for each product are challenging to decentralize to meet the diversification of modern development.
In recent years, electrochemical nitrogen fixation, such as nitrate reduction [
10,
11], nitrite reduction [
12], and dinitrogen gas reduction [
13,
14,
15,
16], has been extensively explored. However, most current studies have focused on the preparation of functionalized electrodes and the detection of trace ammonia, while the further processing of the resulting products has rarely been considered. Moreover, the extraction and refinement of ammonia from aqueous solutions pose significant challenges, which limit its potential for practical utilization. Additionally, the products obtained from electrochemical CO
2RR are mostly gases or liquids, which are not convenient for enrichment and subsequent processing, thereby limiting their large-scale and wide applications. Borrowing from the C-C coupling achieved in the electrochemical CO
2RR process to realize C-N coupling, CO
2 can be drawn into the nitrogen fixation process as an abundant raw material, which provides a prospective way for the improvement of nitrogen recycling.
In this Review, the heterogeneous electrochemical catalytic strategies for
N-containing organic compounds are significantly considered as promising alternatives to the thermochemical processes. While these approaches are still in developmental stages and their underlying reaction mechanisms require further elucidation, a preliminary catalytic system can be established based on known catalytic processes. The initiative mechanism can be provided insight through the summary of these representative cases, and the orientation of further development can be clarified in this field. To this end, several reviews related to the electrochemical co-reduction of CO
2 and nitrogen sources as well as C-N bond formation processes, have been published [
17,
18,
19]. In this literature, the electrochemical C-N bond formation with CO
2 as one of the reactants was first classified according to the N sources and discussed in terms of major products as well as the type of electrocatalysts. Then, the mechanisms were demonstrated including the co-activation of reactants and the formation of C-N bonds. Several theoretical studies were mentioned to provide solid support for the experimental results. Ultimately, the obtained achievements and remaining challenges were summarised to inspire future advances.
2. Nitrous-Integrated CO2 Reduction
Nitrogen oxides (NOx), key contributors to acid precipitation, photochemical haze, and ozone layer depletion, pose severe threats to both ecological systems and public health. The accelerated growth of industrial activities, driven primarily by extensive fossil fuel utilization, has led to an exponential increase in anthropogenic NOx emissions, necessitating immediate remedial measures. The electrocatalytic transformation of NOx into high-value nitrogenous compounds represents a dual-purpose approach that aligns with the principles of green chemistry.
2.1. Urea as the Major Product
From 1996 to 2003, Shibata and co-workers conducted a series of pioneering works toward the N-integrated conversion of carbon dioxide under mild electrochemical conditions [
20,
21,
22,
23]. In their research, various metals (Co, Cr, Mo, Sn, Ag, Cu, Cd, Mn, Ru, Rh, In, Ir, Ni, Pb, Pt, Au, Zn, Tl, and Pd), metal borides (TiB
2, CrB, ZrB
2, NbB
2, MoB, and WB) and metallophthalocyanines (M-Pc, M: Ag, Cr, Mo, Sn, Mn, Rh, Ru, Co, Zn, Pd, Ni, Ir, Tl, Pt, Cu, Au, Cd, In, and Pb) have been adopted as active catalysts and loaded on gas diffusion electrodes for the co-reduction of CO
2 and nitrate or nitrite ions. According to the results, the performance of urea generation is directly related to the efficiency of the sole reduction of CO
2 and nitrate or nitrite. Intriguingly, a linear correlation was found between FE(urea) and [FE(CO)
∗FE(NH
4+)]
0.5 for all three kinds of catalysts (
a) [
24]. Consequently, the generation of C-N bonds was postulated to involve carbon monoxide and ammonia intermediates. Besides, the relatively lower FE
(urea) of nitrate-integrated CO
2 reduction compared to the nitrite one at the same potential may be due to the concentration of
in-situ generated ammonia-like precursor in the reduction of nitrogen oxides.
In recent years, nanostructured materials with specific compositions and surface morphologies have been utilized as working electrodes, driven by the thriving evolution of material chemistry and electrochemistry. Therefore, enhanced efficiency and particular selectivity were achieved in the electrocatalytic processes. Subsequently, as one of the promising electrochemical strategies, the NO
x-integrated electrochemical CO
2 conversion was further developed with newly designed and fabricated electrocatalytic materials. According to the different types of materials used as catalytic electrodes, the existing achievements related to electrochemical NO
x-integrated CO
2 conversion were organized as follows.
2.1.1. Metal and Alloys
The noble metals were treated as the most robust active elements in catalytic chemistry. Although solemn noble metals did not present an effective performance of simultaneous conversion of NO
x and CO
2 according to Shibata’s works, the promoted synthetic efficiency of urea was demonstrated by the modified noble metal-based electrocatalysts. A Te-doped nanocrystalline Pd catalyst was proposed by Feng et al. for the reductive coupling of nitrite and carbon dioxide to produce urea [
25]. When the potential was maintained at −1.1 V versus RHE, the urea production exhibited a Faradaic efficiency of 12.2% with a corresponding nitrogen atom utilization rate of 88.7%. Based on the experimental results and DFT calculations, Te doping optimized the adsorption of CO
2/CO and promoted the reduction of NO
2− to ammonia, thereby providing a convenient condition for gas-reducing and C-N coupling on the interphase for urea formation. The C-N bond was demonstrated to generate between the
∗CO from CO
2 and
∗NH
2 from NO
2− through nucleophilic attack
b). Through a similar reaction pathway, Liu and co-workers also realised electrochemical NO
2-integrated CO
2 conversion using ultra-thin Au-Cu alloy self-assembled nanofibers as the electrocatalyst [
26]. The enhanced FE (24.7%) and superior urea yield rate (64.8 mmol h
−1 g
−1) were mainly attributed to the bimetallic composition, (111)-dominant facets, and 1D-rich defective structures of the material.
Building upon this approach, researchers engineered bimetallic AuPd nanoalloys by embedding palladium into gold nanoparticles, achieving simultaneous electrochemical reduction of nitrate and carbon dioxide for urea production. This catalytic system attained a Faradaic efficiency of 15.6% and a urea generation rate of 3.4 mmol h
−1 g
−1 at an applied potential of −0.5 V versus RHE. [
27]. The incorporation of Pd into Au nanoparticles precisely controlled the synergistic reduction of CO
2 and NO
3− and boosted the following C-N coupling between intermediates. Intriguingly, according to the DFT calculation, the hydroxylamine intermediate was confirmed to react with
∗CO, offering urea with low activation barriers (
c).
. (<strong>a</strong>) High-resolution transmission electron microscopy (HR-TEM) image of PdCu/TiO [<a href="#B24" class="html-bibr">24</a>]. Reproduced with permission. Copyright 2020 Springer Nature Limited. (<strong>b</strong>) HAADF-STEM image and elemental distribution profiles of Te-Pd NCs [<a href="#B25" class="html-bibr">25</a>]. Reproduced with permission. Copyright 2020, ACS Publications. (<strong>c</strong>) Free energies for <sup>∗</sup>CO+<sup>∗</sup>NH<sub>2</sub>OH→<sup>∗</sup>CONH<sub>2</sub> on Pd, AuPd, and Au. In situ surface-enhanced Raman spectroscopy (SERS) of a Cu surface in CO<sub>2</sub> saturated 0.1 M KHCO<sub>3</sub> at OCV with the addition of KCN [<a href="#B27" class="html-bibr">27</a>]. Reproduced with permission. Copyright 2022 Elsevier Publications. (<strong>d</strong>) With 0.01 and 0 ppm of KCN [<a href="#B28" class="html-bibr">28</a>]. Reproduced with permission. Copyright 2022, Elsevier Publications. (<strong>e</strong>) Online DEMS spectra of CO signals over Cu@Zn [<a href="#B29" class="html-bibr">29</a>]. Reproduced with permission. Copyright 2022, ACS Publications. (<strong>f</strong>) Cyclic voltammetric responses of a TiO<sub>2</sub>-Nafion-modified ITO electrode (0.5 cm × 3.5 cm) in 0.1 m KNO<sub>3</sub> (pH 4.5) under Ar atmosphere (green), CO<sub>2</sub> (purple), and bare ITO under CO<sub>2</sub> (blue) at 50 mV s<sup>−1</sup> scan rate [<a href="#B30" class="html-bibr">30</a>]. Reproduced with permission. Copyright 2017, WILEY Publication.
Because of the mysterious coupling function of Cu for the electrosynthesis of multi-carbon products in CO
2RR, Cu-based catalysts were considered one of the most promising candidates in electrochemical C-N coupling reactions [
31,
32]. Krzywda’s team has previously reported that the electrodeposition of copper on a Cu-Ti electrode leads to the NO
3—integrated reduction of CO
2 for the production of urea [
28]. SERS successfully identified the establishment of C-N covalent bonds through the coupling of
∗NH
2 and
∗CO intermediates on the copper electrocatalyst surface. The comparison of Raman spectra demonstrated that C-N coupling was formed on the surface of the Cu, not the residual Cu
2O during the process of electrolytic reduction, generating a unique cyanide intermediate (
d). Although the FE of urea is relatively low in this work, a novel reaction pathway was proposed. To enhance the catalytic performance of a Cu electrode in the electrosynthesis of urea, Meng et al. constructed self-supporting core-shell Cu@Zn nanowires through electroreduction and applied to electrochemical NO
3−-integrated reduction of CO
2 in an aqueous solution [
29] (
e). Under the condition of −1.02 V
vs. RHE, the urea yield rate and FE reached 7.29 μmol·cm
−2·h
−1 and 9.28%, respectively. Employing means of online DEMS, DFT analysis, and in situ ATR-FTIR, the catalytic mechanism was proven similar to that of Te-doped Pd and AuCu. The electron donation from the zinc shell to the copper core promoted the generation and subsequent coupling of
∗CO and
∗NH
2 intermediate species.
Apart from Cu-based materials, other transition metals also possess the ability to trigger the electrosynthesis of urea after elaborate fabrication. Under environmental conditions, urea was formed through electrochemical NO-integrated reduction of CO
2 catalyzed by zinc nanobelts constructed by in-situ electrochemical reduction of ZnO nanosheets [
33]. As an active nitrogen source and one of the crucial intermediates in the electrochemical reduction of nitrite/nitrate, NO facilitated the conversion of CO
2 into urea with less electron and proton demand. A flow cell with gas diffusion layer electrodes and a peristaltic pump further enhances the urea yield rate and FE at 15.13 mmol·h
−1·g
−1 and 11.26%, respectively. According to theoretical calculations, the C-N bond formation took place between
∗NH
2 and
∗CO intermediates.
2.1.2. Metal Oxides and Hydroxides
The semiconductive metal oxides and hydroxides exhibited particular catalytic performance for mediating the electrochemical conversion of inert small molecules. Due to the unique adsorption ability and the intrinsic defects on the surface, CO
2 can be accumulated and activated at the interface of the electrode and electrolyte. A homogeneous porous TiO
2-Nafion composite electrode has been investigated by Shin and co-workers for the electrochemical simultaneous reduction of CO
2 and NO
3− under mild reaction conditions [
30] (
f). The urea was produced along with CO, NH
3, and H
2 as by-products, and 40% of FE
urea was calculated according to the experimental data. Furthermore, nanostructured FeTiO
3 composites demonstrated notable catalytic activity toward urea electrosynthesis during CO
2 reduction coupled with NO
2⁻ incorporation [
34] (
b). Recent work by Anastasiadou and Figueiredo (2024) revealed that CuO
xZnO
x catalysts achieve a 41% Faradaic efficiency at −0.8 V
vs. RHE, attributed to electron transfer between Cu/Zn sites, which lowers the energy barrier for CO
–NH
2 coupling. This exemplifies how bimetallic design enhances interfacial charge transfer for C–N bond formation [
35].
. (<strong>a</strong>) Synthetic procedure illustration of the synthesis of ZnO-V porous nanosheets [<a href="#B36" class="html-bibr">36</a>]. Reproduced with permission. Copyright 2021 Elsevier Publication. (<strong>b</strong>) UV-vis absorption spectra of graph <em>a</em> microwave-synthesized and graph <em>b</em> co-precipitate synthesis FeTiO<sub>3</sub> of CO<sub>2</sub> saturated 0.2 M KNO<sub>2</sub> and 1 M NaHCO<sub>3</sub> solution after reduction [<a href="#B34" class="html-bibr">34</a>]. Reproduced with permission. Copyright 2017 Springer Nature Limited. (<strong>c</strong>) X-ray diffraction (XRD) patterns result for undoped TiO<sub>2</sub> (black) and Cu-TiO<sub>2</sub> (red). Inset: the enlarged view of the XRD pattern at 22°–28° range. The yellow lines indicated the positions of the corresponding peak positions. The red arrow indicates that the XRD peaks of the Cu-TiO₂ sample gradually shift to higher diffraction angles [<a href="#B37" class="html-bibr">37</a>]. Reproduced with permission. Copyright 2020 Elsevier Publication. (<strong>d</strong>) XRD patterns of Vo-CeO<sub>2</sub>-1000, Vo-CeO<sub>2</sub>-75, Vo-CeO<sub>2</sub>-500, and CeO<sub>2</sub>. Reproduced with permission. Copyright 2022, ACS Publication.
As one of the useful defects, oxygen vacancy (V
O) was certificated to promote the catalytic performance in various electrochemical conversion reactions. For the reductive coupling of CO
2 and nitrite, Cao et al. constructed an oxygen vacancy-rich anatase TiO
2 with low-valence Cu-dopant (Cu-TiO
2-V
o) as the electrocatalysts for the synthesis of urea [
37] (
c). The oxygen vacancies in TiO
2 and Cu were instrumental in adsorbing NO
2− and CO
2 and generating
∗NH
2 and
∗CO intermediates, respectively. After the following C-N bond formation, a FE of 43.1% (at −0.4 V
vs. RHE) was attained for urea synthesis. Similarly, an oxygen vacancy-rich ZnO (ZnO-V) nanosheet was also used as a self-supporting electrode by Meng et al. for the electrosynthesis of urea from CO
2 and NO
2− [
36] (
a). Compared to the pristine ZnO, the oxygen vacancies in the porous ZnO nanosheets further enhanced the electrocatalytic performance towards urea production, with FE increasing from 8.10% to 23.26% (at −0.79 V
vs. RHE).
Furthermore, the introduction of oxygen vacancies was also demonstrated to boost the electrochemical CO
2 conversion with NO
3− (
d). By fine-tuning the concentrations of V
O on the CeO
2 nanorods, urea can be provided with 15.7 mmol·h
−1·g
−1 at −1.6 V
vs. RHE [
38]. Based on the validation of in situ SFG spectroscopy and theoretical calculations, V
O can stabilize the reactive intermediates and facilitate selective C-N bond formation. The coupling reaction took place between
∗CO and
∗NO after the reduction of CO
2 and NO
3−, yielding
∗OCNO intermediate. After subsequent alternating protonation, the urea was generated and desorbed from the electrode surface.
Indium hydroxides have been proven effective in the electrochemical conversion of CO
2. Lv and co-workers proposed an In(OH)
3 with (100) facet exposure (In(OH)
3-S) prepared by solvothermal methods for the electrosynthesis of urea [
39]. The conversion of CO
2 with NO
3− was facilitated by the suppression of competing hydrogen emission reactions due to the type of semiconducting behavior change on the In(OH)
3 surface (
a). With the aid of Mott-Schottky measurements, a definite transformation of n-type to p-type semiconductors can be deduced. An ultrahigh FE
urea of 53.4% was obtained at −0.6 V
vs. RHE, and the selectivity of C and N was 82.9% and 100% respectively, because the formation of the solemn nitrogen-containing or carbon-containing by-products was mostly inhibited depending on the facet activity. DFT simulations combined with operando synchrotron radiation FTIR spectroscopy revealed that C-N bond formation between
∗CO
2 and
∗NO
2 intermediates likely initiates at the early reaction stage on In(OH)
3 crystal facets. Furthermore, the
∗CO
2NH
2 intermediate was formed through protonation, and the generation of urea was realized after a second C-N coupling with
∗NO
2 and further protonation. As a continuation, the indium oxyhydroxide with oxygen vacancy (InOOH-V
O) was also solvothermal fabricated and displayed selective C-N coupling toward electrochemical NO
3−-integrated CO
2 conversion, providing urea as the major product with 51% FE [
40]. The oxygen vacancies were verified to facilitate early-stage C-N bond formation and the following protonation processes by regulating the local electronic structure of the surface-active atom (
b).
2.1.3. Single Atomic Catalysts
Benefiting from maximum atomic utilization and defined activity centers, single atomic catalysts exhibit significantly enhanced catalytic activity in a variety of reactions. For example, using sodium chloride as a template, a highly dispersed copper monatomic catalyst was prepared for the simultaneous reduction of CO
2 and NO
3− under electrochemical conditions [
41] (
c). The freeze-drying technique prevented the aggregation of copper. And the single-atom state of copper was validated by HAADF-STEM images. Revealed by the XAS and XANES spectra, the two different coordination structures of Cu in the catalytic SAC material, that is Cu-N
4 and Cu-N
4−x-C
x, synergistically promoted the co-reduction of CO
2 and NO
3−. Based on the DFT calculations, the coupling of
∗CO and
∗NH
2 intermediate occurred at a relatively late stage after the reduction.
In 2022, Zhang’s research team demonstrated that bimetallic Fe-Ni dual-atom catalysts (B-FeNi-DASC) could remarkably enhance urea electrosynthesis efficiency, achieving a production rate of 20.2 mmol h
−1 g
−1. [
42]. A relatively higher FE of 17.8% was also obtained by the catalysis of B-FeNi-DASC, compared with that of single metal and isolated bimetal catalysts. By combining the active site and the coupling site, the bonded Fe-Ni diatoms effectively promoted the NO
3− and CO
2 activation, as well as the C-N coupling processes. The theoretical calculation shows that the B-FeNi-DASC can adsorb and reduce the
∗NO at a low energy level, generating
∗NH intermediate. The operando SR-FTIR measurements demonstrated that the key intermediate
∗NHCONO was formed by the direct coupling of
∗NH and
∗CO and a rapidly second
∗NO connection. The urea was formed subsequently by the PCET process with
∗NHCONO (
d).
2.2. Other Organo-Products
In addition to urea, organic amines can also be available through electrochemical NO
x-integrated CO
2 conversion. A molecular electrocatalyst hybridized by β-tetra-aminophthalocyanine cobalt and carbon nanotube (CoPc-NH
2/CNT) was synthesized for electrochemical NO
3−-integrated CO
2 conversion [
43]. After the characterization towards yielding products in the gas or liquid phase, methylamine was detected as the most abundant molecule among C-N coupling products. Catalyzed by the active CoPc sites, the
∗OCH
2 and
∗OHNH
2 were reductively generated by CO
2 and NO
3− respectively, within which 10e
− and 11H
+ were transferred (
e). A possible route of methylamine formation was elucidated through a series of control experiments, and formaldoxime was identified as the key intermediate, which may be generated from the condensation of hydroxylamine and formaldehyde intermediates. In another study from the same group, ethylamine products can be obtained through the electrochemical co-reduction of CO
2 and NO
3− catalyzed by Cu-base heterogeneous catalysts [
44]. During the electrolysis, the CO
2 was transformed to adsorbed acetaldehyde through 8e reduction and a C-C bond formation process, while the NO
3− was converted to a bounded hydroxylamine intermediate through 6e
− reduction. Similar to the formation of methylamine in the formal study, acetaldoxime was formed through the C-N coupling of acetaldehyde-hydroxylamine condensation. After following reduction and protonation, ethylamine was eventually yielded and can be accumulated by long-time electrolysis.
As one of the promising offerings from electrochemical CO
2RR, formic acid has received widespread attention and has been achieved at a pilot plant scale. As an alternative to direct electrochemical NO
x-integrated CO
2 conversion, Guo and co-workers proposed an electrosynthesis of formamide through the CO
2-derived HCOOH coupling NO
2− co-reduction process [
45] (
f). Derived from Cu
2O nanocubes by electrochemical reduction, the low-coordinated Cu nanocubes exhibited superior catalytic performance for formamide products with 29.7% FE at −0.4 V
vs. RHE. The C-N bond was generated via condensation coupling of
∗CHO and
∗NH
2, which were verified by the
in-situ spectra and theoretical calculations. Furthermore, the developed electrochemical approach enables efficient conversion of acetic acid to acetamide.
In addition, the reductive C-N bond formation was achieved between nitrate ions and oxalic acid that originated from CO
2 reduction [
46]. After verification of the
1H NMR, the glycine was detected as the most valuable C-N coupling product.
. (<strong>a</strong>) Scanning Electron Microscope (SEM) image of In(OH)<sub>3</sub>-S, Scale bars in are 500 nm (unit for reciprocal space) [<a href="#B39" class="html-bibr">39</a>]. Reproduced with permission. Copyright 2021 Springer Nature Limited. (<strong>b</strong>) HR-TEM images of <em>V</em><sub>O</sub>-InOOH [<a href="#B40" class="html-bibr">40</a>]. Reproduced with permission. Copyright 2022, ACS Publication. (<strong>c</strong>) X-ray absorption near-edge structure (XANES) spectra at Cu K-edge for as-synthesized Cu-GS-1000, Cu-GS-900, and Cu-GS-800, compared to reference Cu<sup>II</sup>O (Cu(II)) [<a href="#B41" class="html-bibr">41</a>]. Reproduced with permission. Copyright 2022, WILEY Publication. (<strong>d</strong>) Fourier transform extended X-ray absorption fine structure (FT-EXAFS) spectra of B-FeNi-DASC, I-FeNi-DASC, and Fe-SAC [<a href="#B42" class="html-bibr">42</a>]. (<strong>e</strong>) Potential-dependent product distribution (FE) and total current density [<a href="#B43" class="html-bibr">43</a>]. (<strong>f</strong>) Cu K-edge extended XANES spectra of Cu<sub>2</sub>O, Cu foil, and ER-Cu [<a href="#B45" class="html-bibr">45</a>]. Reproduced with permission. Copyright 2021, 2021 Springer Nature Limited.
3. Dinitrogen-Integrated CO2 Reduction
As the most abundant gas in the atmosphere, nitrogen is used in a variety of natural and artificial nitrogen fixation processes. However, these processes either cannot be mass-produced industrially or are energy-intensive, which has an adverse effect on the development of human beings. Meanwhile, the emerging photo- or electro-chemical mediated fixation of N
2 is limited by low conversion efficiency and production enrichment difficulties for practical use [
47,
48,
49,
50]. As a promising alternative, carbon dioxide and nitrogen can be co-reduced and coupled to form C-N bond-containing products under electrochemical conditions (
a). The challenging adsorption of both gas substrates and the subsequent C-N formation requires precise construction of functional materials and fine-tuning of surface electronic distribution, and there have been several successful cases [
51]. To date, the only product formed through C-N coupling is urea. The following content was discussed in relation to different types of electrocatalysts and methods adopted to enhance the reactive efficiency and catalytic selectivity.
3.1. Metallic Alloys
Alloys, one of the robust catalysts with outstanding synergic effects in various catalysis, also presented robust catalytic performance in electrochemical N
2-integrated CO
2 conversion. As a unique catalytic site, Cu is claimed to possess a coupling function during the catalysis process, proven by various electrochemical CO
2RR toward C2 production [
52]. Therefore, introducing Cu element into alloy materials is promising in boosting electrochemical C-N coupling reactions. In addition, defect engineering is crucial for such alloy catalysts in aqueous electrochemical reactions, due to the indispensable enhancement of adsorption of insoluble feed gases. In 2020, Chen and co-workers used PdCu nanoparticles loaded on titanium dioxide to electrocatalyst the reduction and coupling of N
2 with carbon dioxide to form urea. −0.4 V
vs. RHE [
53]. The system achieved a urea production rate of 3.36 mmol g
−1 h
−1 with a FE of 8.92%. The incorporation of alloy nanoparticles was found to strengthen nitrogen and carbon dioxide adsorption, thereby improving the overall catalytic performance (
b). Due to the bimetallic synergistic effect and electronic optimization, the catalyst exhibits superior catalytic activity, enabling carbon-nitrogen coupling to form urea. The composite material exhibited a dual function in the co-reduction of CO
2 and N
2, and the C-N bond formation was further boosted by the Cu counterparts in the alloy. Recently, through the chemical reduction of a mixture of ammonium bismuth citrate and copper chloride, a defective Cu-Bi alloy was synthesized and utilized as electrocatalysts in the co-reduction of N
2 and CO
2 (
c) by Wu et al. [
54].
3.2. Hybrid Materials
Heterojunction nanomaterials possess a dual active site, exhibiting synergistic effects on electrocatalytic transformations. On the surface of well-defined catalytic materials, nucleophilic and electrophilic sites are dispersed, which not only facilitates the adsorption and activation of inert gases such as N
2 and CO
2 but also promotes the subsequent coupling process between reduced intermediates. In this context, Yuan and co-workers designed several hetero-structured nano-materials to enhance C-N bond formation towards the generation of urea. The well-designed Bi-based Mott-Schottky heterostructure (Bi-BiVO
4) [
55] (
d) and the perovskite hybrids (BiFeO
3-BiVO
4) [
56] (
e) were fabricated and applied in the electrochemical conversion of N
2 and CO
2 into urea under ambient conditions. At −0.4
vs. RHE in 0.1 M KHCO
3, the FE of urea was 12.55% and 17.18%, respectively. In both cases, The BiVO
4 acted as the electrophilic catalytic site, which adsorbed the N
2 molecule with a side-on configuration (
∗N=N
∗). According to the free energy calculation, the side-on bound N
2 was more stable and negative than the end-on configuration. Additionally, CO
2 molecules undergo adsorption and activation at the nucleophilic Bi/BiFeO
3 interfaces, resulting in the formation of the key
∗CO intermediate. Subsequently, the C-N coupling occured between the negative
∗N=N
∗ intermediate and the positive
∗CO intermediate, yielding
∗NCON
∗ with relatively low energy barriers. The formation of urea preferentially underwent the distal protonation process. The catalytic performance can be further promoted by introducing an ionic liquid electrolyte to enhance CO
2 solubility in the system.
. (<strong>a</strong>) The distributions of <em>R</em><sup>2</sup> and slope deviation under all tests by the urease method [<a href="#B51" class="html-bibr">51</a>]. Reproduced with permission. Copyright 2022, WILEY Publication. (<strong>b</strong>) HR-TEM image of Pd<sub>1</sub>Cu<sub>1</sub>/TiO<sub>2</sub>-400. Scale bar: 2 nm. Reproduced with permission. Copyright 2020 Springer Nature Limited. (<strong>c</strong>) Selected area electron diffraction (SAED) of defective Cu-Bi. Each circle represents the collection of the same crystal plane of different crystal grains [<a href="#B54" class="html-bibr">54</a>]. Reproduced with permission. Copyright 2022 Elsevier Publication. (<strong>d</strong>) XRD patterns analysis of Bi-BiVO<sub>4</sub> [<a href="#B55" class="html-bibr">55</a>]. Reproduced with permission. Copyright 2021, WILEY Publication. (<strong>e</strong>) XRD pattern analysis of BiFeO<sub>3</sub>/BiVO<sub>4</sub> [<a href="#B56" class="html-bibr">56</a>]. Reproduced with permission. Copyright 2021, RSC Publication. (<strong>f</strong>) Raman spectra of the pristine Ni<sub>3</sub>(BO<sub>3</sub>)<sub>2</sub>-250, Ni<sub>3</sub>(BO<sub>3</sub>)<sub>2</sub>-150, and Ni<sub>3</sub>(BO<sub>3</sub>)<sub>2</sub> catalysts [<a href="#B57" class="html-bibr">57</a>]. Reproduced with permission. Copyright 2008, RSC Publication.
Furthermore, by fine-tuning the electron distribution and functional modifying components, transition-metal-based materials exhibit incomparable electrocatalytic performance for the selective activation of reactant molecules and C-N coupling ability in urea synthesis. Following a similar synthetic pathway to urea as the Bi-based heterostructures, artificial frustrated Lewis pairs (FLPs) have been demonstrated to be the superior catalysts for electrochemical co-reduction of CO
2 and N
2 for urea production through C-N bond formation. The surface electrostatic potential analysis has demonstrated the positive effect of artificial FLPs on adsorption, activation, and C-N coupling reaction steps during the electrochemical urea synthesis (
f). Both CO
2 and N
2 can be firmly absorbed and smoothly activated by the neighboring Lewis acid and base active sites. Conspicuously, the C-N coupling can be facilitated through σ-orbital carbonylation strategy by the empty e
g orbital of the catalytic metal site at a low-spin stat (
). As a proof of concept, a flower-like nickel borate was fabricated and applied to the electrosynthesis of urea, where adjacent Ni atom and hydroxyl group served as Lewis acid and base, respectively [
57]. The annealing treatment introduced low-spin Ni²⁺ sites and adjacent hydroxyl groups, achieving a FE of 20.36% at −0.5 V
vs. RHE and a urea yield rate of 9.70 mmol·h
−1·g
−1. In addition, a rice-like InOOH nanocrystal was also constructed, modified by annealing treatment, and utilized as the catalytic electrode for the N
2-integrated CO
2 conversion into urea, with 20.97% of FE and 6.85 mmol·h
−1·g
−1 of yield rate [
58] (
a). In another example, a conductive MOF Co-PMDA-2-mbIM with host-guest molecular interaction attained the highest FE of 48.97% to date in the electrosynthesis of urea with N
2 and CO
2 [
59] (
b). The guest molecules were demonstrated to regulate the spin-state of Co, providing an empty e
g orbital as the electrophilic region that facilitated the reduction of N
2. After the reduction of CO
2 at the neighboring nucleophilic region, the C-N coupling was triggered through the σ-orbital carbonylation strategy that was mediated by the empty e
g orbital of Co as well. More recently, a Cu-based MOF, Cu-HHTP, (
c) was also verified as an effective and robust electrocatalysts for the co-reduction of CO
2 and N
2 for the synthesis of urea [
60]. After regulation of spin-state through the oxidation of isolated Cu species in the MOF, the catalytic performance was enhanced, obtaining a FE of 23.09% at −0.6 V
vs. RHE and a high urea yield of 7.780 mmol h
−1 g
−1. The empty d orbitals exhibited superior activation effect for the inert N
2 molecules and the low spin-state favorably promoted the C-N coupling process, thus improving the outstanding synthetic performance toward electrochemical urea production.
Due to the perspective achievement of metal phthalocyanine-based materials [
61] in both electrochemical CO
2RR and N
2RR, copper phthalocyanine nanotubes (CuPc NTs) were constructed by Mukherjee and co-workers for electrochemical generation of urea from N
2 and CO
2 [
62] (
d). Thanks to the multiple active sites of CuPc, the CuPc NTs exhibited the FE of 12.99% at −0.6 V
vs. RHE and the urea yield rate of 143.47 μg h
−1 mg
cat−1. The experimental results and DFT calculations show that the pyridinic-N1 and Cu sites were responsible for CO
2 and N
2 reduction, respectively.
. (<strong>a</strong>,<strong>b</strong>) Projected density of states (pDOS) profiles for N<sub>2</sub> adsorption on (<strong>a</strong>) the Ni Lewis acid center and (<strong>b</strong>) the O Lewis base site (within OH⁻ groups) of engineered frustrated Lewis pairs (FLPs), accompanied by crystal orbital Hamilton population (pCOHP) analyses of (<strong>a</strong>) Ni-N and (<strong>b</strong>) O-N bonding interactions (right panels), elucidating the gas activation mechanism. (<strong>d</strong>,<strong>e</strong>) Corresponding pDOS spectra for CO<sub>2</sub> binding at (<strong>d</strong>) Ni and (<strong>e</strong>) O sites, with pCOHP evaluations of (<strong>d</strong>) Ni-O and (<strong>e</strong>) C-O bond formation (right panels). Schematic representations depict the charge transfer processes between FLPs and (<strong>c</strong>) N<sub>2</sub> or (<strong>f</strong>) CO<sub>2</sub> molecules, highlighting donor-acceptor interactions. An asterisk “<sup>∗</sup>” before an element symbol indicates that the element is an adsorbed atom on the adsorption site, not an atom of the substrate material itself. The “<sup>∗</sup>” in the superscript of a Greek letter represents an antibonding orbital [<a href="#B57" class="html-bibr">57</a>]. Reproduced with permission. Copyright 2008, RSC Publication.
3.3. Composite Methods
To overcome the poor aqueous solubility of N
2 and CO
2, electrochemical N
2-integrated CO
2 reduction at high pressure can be a viable option to enhance the catalytic performance. In 2016, Kayan and co-workers fabricated a Pt electrode covered with conductive polymers for N
2-integrated CO
2 reduction [
63]. Under the relatively high pressure of the given gas, namely 30 bar CO
2 and 30 bar N
2, the C-N coupling product was obtained as urea with more PPy coated on the electrode in an aqueous solution (
f). The chemically generated ammonium carbamate, produced under high pressure, was supposed to be the key intermediate for producing urea, thus the production of urea is primarily related to ammonia that in-situ formed from N
2 reduction.
It has been widely recognized that photochemical assistance can significantly enhance electrocatalytic activity. In this context, Bharath and co-workers proposed a plasmon-enhanced photo-electrochemical process for CO
2 and N
2 into urea [
64]. The plasmonic Au nanostructures were synthesized, optimized, and adopted as catalytic materials. Upon visible and near-infrared light illumination, the Au-based electrocatalyst exhibited significantly improved activity, achieving a urea production rate of 98.5 μg h
−1 mgcat
−1 with 22.7% Faradaic efficiency at −0.7 V
vs. RHE (
e).
3.4. Theoretical Study
To address the challenging problems in the electrocatalytic synthesis of urea from N
2 and CO
2 co-reduction under mild reaction conditions, DFT computations were carried out based on first-principles via the Vienna ab initio simulation package (VASP). The projector-augmented wave (PAW) approach and PBE-GGA functional were employed to characterize ion-electron interactions and exchange-correlation effects, respectively. With a rectangular lattice and planar anisotropic structure, the conductive 2D MBenes (Mo
2B
2, Ti
2B
2, and Cr
2B
2) were theoretically revealed by Li et al. as efficient electrocatalysts for urea synthesis [
65]. Based on the calculation result, the urea synthetic pathway was deduced to start from N
2 adsorption with a side-on configuration and the CO
2 binding to the neighboring bridge site. Then, the C-N bond was subsequently formed between the
∗N
2 and
∗CO intermediate, generating
∗NCON as the key intermediate. At last, the urea was obtained after alternative hydrogenation steps. It is worth noting that urea desorption was an endothermic process, not the exothermic process reported by the experimental electrocatalysts mentioned above. Another planar CuB
12 monolayer was investigated and claimed as a promising catalyst for the electrosynthesis of urea through the
∗NCON hydrogenation as well. After a thoroug exploration of the possible reaction mechanism for urea production, the C-N bond formation was released between
∗CO and
∗NHNH intermediates rather than the
∗NCON pathway [
66]. Meanwhile, conductive dual-Si doped g-C
6N
6 nanosheets [
67] and a vanadium/nitrogen co-doped carbon nanocrystal [
68] were revealed to be highly efficient for electrocatalytic urea generation from N
2 and CO
2 through the
∗NCON hydrogenation pathway. More recently, an atomic dispersed dual-metal catalyst constructed on N-doped graphene, namely M
2@N
6G, was theoretically studied for latent application in the electrosynthesis of urea [
69]. After systematical exploration, 8 optimized catalytic materials were verified to promote the C-N coupling reaction through the
∗NCON pathway. The principal descriptor (
ΔE(
∗NCONH)) was demonstrated for future evaluation of the investigation of the electrosynthesis of urea.
. (<strong>a</strong>) Electron-density isosurface of CO<sub>2</sub> (left) and N<sub>2</sub> (right) molecules [<a href="#B58" class="html-bibr">58</a>]. Reproduced with permission. Copyright 2022 Elsevier Publication. (<strong>b</strong>) corresponding product distributions of CO (cyan), NH<sub>3</sub> (grey), H<sub>2</sub> (blue), and urea (pink) with N<sub>2</sub> and CO<sub>2</sub> as the feed gases at various potentials using Co-PMDA-2-mbIm [<a href="#B59" class="html-bibr">59</a>]. Reproduced with permission. Copyright 2008, RSC Publication. (<strong>c</strong>) The TEM and EDS mapping images of Cu<sup>III</sup>-HHTP (scale bar = 200 nm). Reproduced with permission. Copyright 2023 Springer Nature Limited. (<strong>d</strong>) XRD pattern of CuPc NTs [<a href="#B62" class="html-bibr">62</a>]. Reproduced with permission. Copyright 2022, WILEY Publication. (<strong>e</strong>) Free energy diagram for N<sub>2</sub>CO<sub>2</sub>RR via alternation and distal pathway on Au NSs [<a href="#B64" class="html-bibr">64</a>]. (<strong>f</strong>) The SEM images of PPy coated Pt electrode [<a href="#B63" class="html-bibr">63</a>]. Reproduced with permission. Copyright 2022, 2016 Elsevier Publication.
4. Ammonia- and Amine-Integrated CO2 Reduction
4.1. Ammonia-Integrated CO2 Reduction
Ammonia serves as a crucial industrial chemical with significant economic importance worldwide. In addition to the applications in the synthesis of fertilizer, disinfectant, and refrigerant, ammonia can also act as an efficient hydrogen storage medium in the hydrogen energy industry and a robust nitrogen source in electrochemical energy conversion. Therefore, several explorations were conducted for the ammonia-integrated electrocatalytic conversion of CO
2 with amides and amino acids as the most valuable products.
4.1.1. Amide Formation
Catalyzed by Cu nanoparticles on a gas diffusion layer electrode, the formation of a C-N bond was demonstrated by Jiao and co-workers through co-electrolysis of CO
2-derived CO and NH
3 [
70]. Among the C-C and C-N coupling products, the acetamide can be selectively generated with nearly 40% FE (
a). According to the experimental and calculation results, after the C-C coupling between two adjacent
∗CO intermediates, thermodynamically favored dehydration and C-N bond formation subsequently occurred, generating acetamide as the final product. Furthermore, amines were also fitted in this C-N coupling process, yielding corresponding
N-substituted amides with high selectivity.
Similarly, with the adaptation of a gas diffusion electrode, a C-N coupling was realized at the triple-phase boundary, where the gaseous CO
2 and liquid-phase ammonia reacted over a solid Cu catalyst [
71]. Alkaline electrolytes were employed to minimize the competing HER, and the amides were detected by the NMR spectra with modest FE. Meanwhile, a thicker catalyst loading could promote the FE value for producing acetamide, while having little effect on formamide. For the generation of acetamide, the C-C coupling between reduced
∗CO intermediates, the dehydration, and the C-N coupling between ketene intermediate and ammonia were the crux as well. Additionally, the nitrite and nitrate ions were confirmed to be potential sources of nitrogen in this process.
4.1.2. Amino Acid Formation
Most recently, C-N bond formation between CO
2 and NH
4+ for the synthesis of amino acids was discovered by Fang and co-workers [
72]. By the fabrication of a chiral Cu film catalyst in the presence of histidine, a highly enantiomeric Serine product was obtained (
c). According to the experimental and calculation results, the 3-hydropyruvic acid was first formed through multiple C-C coupling steps. Then the amino acid was generated via the amination with ammonia. Although the electrolysis was conducted under high pressure, and a modest FE was obtained compared to formic acid and ethanol, this process undoubtedly integrates the synthesis of small biological molecules, CO
2 resource utilization, and electrochemical technology, thus offering a novel orientation for the electrochemical conversion of CO
2.
. (<strong>a</strong>) Schematic diagram showing the formation of C–N bonds through the electrolysis of CO induced by ammonia [<a href="#B70" class="html-bibr">70</a>]. Reproduced with permission. Copyright 2019 Springer Nature Limited. (<strong>b</strong>) Reaction of amines 1g and 1a with CO<sub>2</sub> and EtI in MeCN−TEAP-electrolyzed solutions. Divided cells, Pt cathode and anode, with a current density of <em>I</em> = 16 mA cm<sup>−2</sup>. Electrolysis was carried out under constant current control. The yields (based on the starting amine) of isolated carbamates 2g and 2a versus <em>Q</em> (number of Faradays per mole of amines supplied to the electrodes) according to procedure A [<a href="#B73" class="html-bibr">73</a>]. Reproduced with permission. Copyright 2003, ACS Publication. (<strong>c</strong>) Corresponding atomic models of transition states and intermediates in the energy curves on (111) and (653) surfaces [<a href="#B72" class="html-bibr">72</a>]. Reproduced with permission. Copyright 2023 Elsevier Publication. (<strong>d</strong>) N and Cu contents in Cu-N-C materials [<a href="#B74" class="html-bibr">74</a>]. Reproduced with permission. Copyright 2021, WILEY Publication.
4.2. Amine-Integrated CO2 Reduction
4.2.1. Alkylation of Amines
In synthetic chemistry, when reacted with an amine, the CO
2 can act as a methylation agent to generate substituted amines. Rooney and coworkers reported that
N-methylated products can be obtained through amine-integrated electrochemical reduction of CO
2 by phthalocyanine cobalt molecular catalysts supported by carbon nanotubes (CoPc/CNT) [
75]. In 0.1 M KHCO
3 aqueous solution, the aniline, fatty amine, hydroxylamine, and even hydrazine were suitable nitrogen sources, while methylation does not occur with ammonium ions. It is worth noting that the
N-methylaniline was also obtained through the co-reduction of nitrobenzene and CO
2. The C-N bond was formed by the condensation between the N nucleophile and the electrophilic
∗OCH
2, generated from the reduction of CO
2.
4.2.2. Carboxylation of Amines
As one of the promising approaches for the synthesis of carbamates, the electrochemical conversion of CO
2 with amines and alkylating reagents eliminates the use of hazardous chemicals and harsh reaction conditions, thus providing a green route for CO
2 utilization. As early as 1996, Casadei and co-workers reported the electrochemical activation of CO
2 for the synthesis of organic carbamates, a type of organic compound used in pesticides, medicines, and organic modifiers [
76]. As a continuation, Faroci and co-workers proposed an efficient electrochemical synthesis of organic carbamates from
−CH
2CN/CO
2 carboxylation reagent. The reaction was conducted in the cathodic chamber of a divided cell, and the CO
2 molecules were attacked by the in-situ reduced amine intermediate (
b), namely the carboxylation of amines [
73]. Thereafter, the efficiency of this procedure was further facilitated by conducting the cathodic reduction of CO
2 in ionic liquid solutions [
77]. Furthermore, a combination of electrooxidation of aryl ketones and electrosynthesis of carbamates from CO
2 and amine was realized by Wang et al. [
78]. The aryl ketone was first oxidized and then substituted by the in-situ generated molecular iodine. Then, the yielding organo-iodide was consumed as the alkylating agent in the electrosynthesis of carbamates. In 2021, Li and co-workers explored the catalytic performance of Cu SACs for the electrosynthesis of carbamates [
74]. The Cu-N-C nanosheets were fabricated through the pyrolysis of Cu-MOF precursors (
d). The electrolysis was conducted in a divided cell under constant electric current. The optimal reaction condition was precisely screened, and the tolerance of substitutions was tested. It is reasonably speculated that the abundant high-dispersive Cu sites promoted the C-N bond formation within the catalytic mechanism.
5. Conclusions and Outlooks
Powered by sustainable energy sources, ambient-temperature electrocatalytic synthesis of functionalized organic compounds through nitrogen-assisted CO
2 transformation represents a green and energy-efficient approach. This comprehensive review systematically examines recent breakthroughs in CO
2 electroreduction facilitated by diverse nitrogen-containing precursors for selective C-N coupling. Diverse products can be obtained efficiently and selectively, such as urea, amine, amide, carbamate, and amino acids. For their generation, types of nano-engineered electrocatalysts with specific effectiveness and robustness were also demonstrated. Furthermore, the mechanisms of C-N coupling varied depending on the nitrogen-containing substrates and reaction conditions. For instance, the C-N bond formation was enabled from
∗CO
2 and
∗NO
2 to form the key
∗CO
2NO
2 intermediate for further protonation and reduction. Furthermore, the reduced
∗CO or
∗COOH could also directly couple with protonated
∗NH
2. In some cases, the C-N coupling emerged from the interaction between the
∗CO and
∗N
2 or released CO, generating
∗NCON
∗ intermediate for subsequent hydrogenation. The C-C coupling took place before the C-N bond formation step for multiple-carbon-containing products, such as acetamide and amino acid. Meanwhile, to harvest products with higher value, exogenous auxiliary strategies were also used, like high-pressure and light irradiation. Moreover, CO
2 can also act as C1 building blocks for the decoration of amines, generating alkylation or carboxylation products under electrocatalysis conditions.
Although the electrocatalytic CO
2 reduction reaction during the experimental stage could operate stably at a current density of 100 mA·cm
−2 for over 1000 h [
79], with an FE efficiency exceeding 88.5% [
80], there are still challenges that need to be overcome for the industrial application of electrochemical CO
2 conversion [
81]. For instance, competitive side reactions, such as CO, H
2, NH
3 generation, as well as C-C bond formation were inevitable, especially under high overpotential and high operation current density. On the other hand, the precisely manufactured electrocatalysts have been costly and insufficiently stable to date. Therefore, the emerging technology of CO
2 conversion through electrocatalytic C-N coupling still demands robust efficiency and outstanding selectivity.
As revealed by previous works, nanoengineering of electrocatalysts plays an important role in constructing multifunctional catalytic active sites to precisely control reaction pathways. The synergy effects are essential for the activation of inert molecules and stabilization of key intermediates, thereby the realization of C-N bond formation. Beyond material innovation, integrating computational modeling with machine learning approaches can accelerate the design of higher-performance catalysts and more efficient reaction pathways. Besides, the details of plausible reaction mechanisms can also be influenced by the optimization of electrolytes, thus resulting in complex difficulties for the exploration of the actual pathway toward desired C-N coupling products. In this manner,
in-situ characterization technologies could provide us with more detailed information on the reaction mechanism, which may offer abundant evidence for the improvement of catalysts. It is worth noting that several intermediates mentioned in the DFT calculations were not observed in the in-situ spectroscopic measurements. Therefore, to practically realize the industrial application of CO
2 conversion through the electrocatalytic C-N coupling technique requires more attention and dedication in the investigation of the fabrication of functional catalysts and the identification of key intermediates.
Acknowledgments
We express our thanks for funding support from the Fundamental Research Funds for Public Universities in Liaoning (LJ232410140033), the Open Foundation of State Key Laboratory of Biobased Transportation Fuel Technology, Zhejiang University (2025-002), Natural Science Foundation of Liaoning Province (general program) (2020-MS-137).
Author Contributions
Y.G.: Writing—Initial draft, research, form analysis. Z.L.: Review and edit the written content. L.Z.: Review and edit the written content, conduct research. D.F.: Review and edit the written content, supervise, manage resources, project management, secure funding, concept conception. C.G.: supervise, manage resources, project management.
Ethics Statement
Not applicable.
Informed Consent Statement
Not applicable.
Funding
This research was funded by the Fundamental Research Funds for Public Universities in Liaoning (LJ232410140033), the Open Foundation of State Key Laboratory of Biobased Transportation Fuel Technology, Zhejiang University (2025-002), Natural Science Foundation of Liaoning Province (general program) (2020-MS-137).
Declaration of Competing Interest
The author declares that at present, there are no potential conflicts of interest or personal relationships that could affect the research results reported in this article.
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