Advances in Semiconductor-Based Nanocomposite Photo(electro)catalysts for Nitrogen Reduction to Ammonia
Abstract
:1. Introduction
2. Nitrogen Reduction Reaction
3. Challenges of NRR
3.1. Low Utilization of Light Energy
3.2. Low Separation Rate of Photogenerated Carriers
3.3. N2 Adsorption and Activation Difficulties
3.4. Hydrogen Analysis Competition
3.5. Other Problems in NRR
4. Modification Strategies for the Photo(electro)catalysts
4.1. Morphology Modulation
4.1.1. Photocatalyst
4.1.2. Electrocatalyst
4.2. Heterostructure Construction
4.3. Introduction of Vacancies
4.3.1. Photocatalyst
4.3.2. Electrocatalyst
4.4. Cocatalyst Addition
4.5. Computational Modeling
5. Conclusions and Prospects
- 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 photocatalytic 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.
- 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.
- 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 develo**. It is necessary to conduct more in-depth thermodynamic and kinetic studies to understand 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 theoretical research. Therefore, it is necessary to further improve the calculation method and model of NRR on the surface of non-homogeneous catalysts to combine theoretical calculations and experiments and to provide further guidance for designing electrocatalyst structures.
- 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 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
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
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Reaction | Reduction Potential (V) | Equation |
---|---|---|
H2O → 1/2O2 + 2H+ + 2e− | 0.81 | 1a |
2H+ + 2e− → H2 | −0.42 | 1b |
N2 + e− → N2- | −4.16 | 1c |
N2 + H+ + e− → N2H | −3.2 | 1d |
N2 + 2H+ + 2e− → N2H2 | −1.10 | 1e |
N2 + 4H+ + 4e− → N2H4 | −0.36 | 1f |
N2 + 5H+ + 4e− → N2H5+ | −0.23 | 1g |
N2 + 6H+ + 6e− → 2N2H3 | 0.55 | 1h |
N2 + 8H+ + 8e− → 2N2H4 | 0.27 | 1i |
Photocatalyst | Morphological Characteristics | Preparation Method | Nitrogen Source | Sacrificial Agent | Light Source | Ammonia Yield | References |
---|---|---|---|---|---|---|---|
Ag/PM-CdS(e) | Nanospheres (diameter of about 14.2 nm) | Hydrothermal–Etching | N2 | - | λ > 420 nm | 0.343 μg·h−1·mg−1 | [41] |
AgCl/δ-Bi2O3 | Nanosheets (thickness of about 2.7 nm) | Hydrothermal precipitation method | N2 | - | λ > 420 nm | 606 μmol·h−1·g−1 | [42] |
BOC/OV3 | Micro-nanosheets (<10 × 10 nm) | Room temperature reaction-reduction | N2 | Na2SO3 | λ > 400 nm | 1178 μmol·L−1·g−1·h−1 | [43] |
Ru-In2O3 | Hollow peanut structure | Air Calcination | N2 | Methanol | UV-vis | 44.5 μmol·g−1·h−1 | [40] |
NYF/NV-CNNTs | Nanotubes | Solvothermal method | N2 | Ethanol | λ~980 nm or > 420 nm | 1.72 mmol·L−1·gcat−1 or 5.30 mmol·L−1·gcat−1 | [44] |
Au/HCNS-NV | Mesoporous hollow spheres | Templating agent calcination-reduction | N2 | Methanol | λ > 420 nm | 783.4 μmol·h−1·gcat−1 | [45] |
1T’-MoS2/CNNC | Nanocages | Hydrothermal method | N2 | Methanol | UV-vis | 9.8 mmol·L−1·h−1·g−1 | [46] |
Nv&Od-CN | Porous hollow prisms | Low-temperature hydrothermal–calcination | N2 | Methanol | λ > 420 nm | 118.8 mg·L−1·h−1·gcat−1 | [47] |
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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
Zuo C, Su Q. Advances in Semiconductor-Based Nanocomposite Photo(electro)catalysts for Nitrogen Reduction to Ammonia. Molecules. 2023; 28(6):2666. https://doi.org/10.3390/molecules28062666
Chicago/Turabian StyleZuo, Cheng, and Qian Su. 2023. "Advances in Semiconductor-Based Nanocomposite Photo(electro)catalysts for Nitrogen Reduction to Ammonia" Molecules 28, no. 6: 2666. https://doi.org/10.3390/molecules28062666