Nitrogen Electroreduction Research Articles

Multifunctional Strategies of Advanced Electrocatalysts for Efficient Urea Synthesis.

The electrochemical reduction of nitrogenous species (such as N2, NO, NO2 -, and NO3 -) for urea synthesis under ambient conditions has been extensively studied due to their potential to realize carbon/nitrogen neutrality and mitigate environmental pollution, as well as provide a means to store renewable electricity generated from intermittent sources such as wind and solar power. However, the sluggish reaction kinetics and the scarcity of active sites on electrocatalysts have significantly hindered the advancement of their practical applications. Multifunctional engineering of electrocatalysts has been rationally designed and investigated to adjust their electronic structures, increase the density of active sites, and optimize the binding energies to enhance electrocatalytic performance. Here, surface engineering, defect engineering, doping engineering, and heterostructure engineering strategies for efficient nitrogen electro-reduction are comprehensively summarized. The role of each element in engineered electrocatalysts is elucidated at the atomic level, revealing the intrinsic active site, and understanding the relationship between atomic structure and catalytic performance. This review highlights the state-of-the-art progress of electrocatalytic reactions of waste nitrogenous species into urea. Moreover, this review outlines the challenges and opportunities for urea synthesis and aims to facilitate further research into the development of advanced electrocatalysts for a sustainable future.

Metal nitrides as electrocatalysts in green ammonia synthesis

Green ammonia is assumed to be an important part of the European hydrogen economy and one of the most important substrates of chemical industry. The future development of its manufacturing processes can be related to the electrocatalytic studies yielding in the development of the catalytic materials that would effectively break the nitrogen-nitrogen bond to successfully drive the N2RR—a process of molecular nitrogen electroreduction to ammonia. Molecular nitrogen is characterized with strong triple bond energies (942 kJ/mol) which leading into large dissociation energy of N2 (9,76 eV) and also large energy barrier of the first step of triple bond dissociation 410 kJ/mol (4,25 eV). Those large energies makes reduction to ammonia an extremely difficult task. Metal nitrides of d and f block became in interest due to their activity in ammonia production from molecular nitrogen and hydrogen. Practically all the transition elements occurs in one of the four types of crystalline structures: regular, regular face cantered, hexagonal and hexagonal close packed. The reactions of these metals with nitrogen (or ammonia) typically yields in nitride compounds of an identical type of crystalline structure as the initial metal. Dealing with single metal systems, their ternary counterparts and metal–metal nitride heterostructures, the presented review shows that nitrides are promising groups of electrocatalytic materials. Being property-prone to their internal structural features such as non-stoichiometry and correlated concentration of nitrogen vacancies, metal nitrides are a good candidate for joined investigations spanned between electrochemistry, inorganic chemistry and material engineering.

Electrocatalytic reduction of nitrate to ammonia over activated carbon-supported copper-iron bimetallic catalyst synthesized by hydrothermal co-precipitation method

Ammonia synthesis via electrocatalytic reduction of nitrate is a promising approach for green ammonia production. However, this process limited by multiple reaction pathways and NO3− adsorption over electrocatalyst surface. Herein, copper-iron bimetallic catalysts with different atom ratios of Cu/Fe (Cu/Fe = 10/0, 7/3, 5/5, 3/7 and 0/10) and activated carbon as supporter (CuFeOx/AC) were synthesized through hydrothermal co-precipitation method for catalytic reduction of nitrate. Synergistic effects between the Cu and Fe were observed in the copper-iron bimetallic catalysts and an appropriate atom proportion of Cu/Fe was benefit to accelerate the adsorption and electrocatalytic kinetics of nitrate reduction to *NO2 and *NO2 hydrogenation to·NH3 through electron redistribution. The catalyst of 7Cu3FeOx/AC presented the best catalytic performance in nitrogen electroreduction reaction for ammonia synthesis, with an NH3 yield rate of 2091 μg h−1 mgcat−1 and a faradaic efficiency of 76 % at −0.8 V vs. reversible hydrogen electrode. The 7Cu3FeOx/AC also exhibited excellent cycle ability and long-term durability whose NH3 yield rates maintained as high as 1476 and 2326 μg h−1 mgcat−1 after 9 cycles and 10 h durability measurement, respectively. The nitrate reduction behavior over 7Cu3FeOx/AC proceeded with a series of deoxygenation reactions as follows: NO3− → *NO3 → *NO2 → *NO → *NOH → *NH2OH →·NH3. With the above excellent properties, the 7Cu3FeOx/AC may prove to be a promising electrocatalyst for ammonia synthesis via nitrogen electroreduction reaction.

Co-adsorbate-mediated nitrogen electroreduction on two-dimensional W@BC4N single-atom catalyst: Insight from first-principles

Co-adsorbed intermediates ubiquitous on catalyst surface play an important role in mediating the reaction pathway. Herein, we systematically explore the co-adsorbate (*N2 and *H)-mediated nitrogen electroreduction reaction (NRR) on graphene-like W@BC4N single-atom catalyst (SAC) using density-functional theory (DFT) calculation and ab-initio molecular dynamics (AIMD) simulation. The results reveal that the multiple NRR pathways dependent on adsorption mode of *N2 can cross over with one another. The proton-coupled electron transfer (PCET) in NRR is likely to couple with the intermolecular hydrogen-transfer. With three *N2 and two *H as spectators, NRR can proceed via a mixed consecutive-enzymatic mechanism, where the 6th PCET, *NH2 + (H+ + e-) → *NH3, is the potential-limiting step with UL = -0.72 V, larger than those (UL = -0.47 V, UL = -0.52 V and UL = -0.67 V) absence of the co-adsorbed *N2. Nonetheless, the co-adsorbed *N2 can facilitate the desorption of *NH3, beneficial to catalytic cycling. Given the steric hindrance of the co-adsorbed NHx intermediates, hydrazine (N2H4) is most likely to be produced during NRR. With W single-atom site working synergistically with the adjacent B site, W@BC4N has demonstrated the high promise for driving NRR.

Fluorine Domains Induced Ultrahigh Nitrogen Solubility in Ionic Liquids.

Fluorinated ionic liquids (ILs) are well-known as electrolytes in the nitrogen (N2) electroreduction reaction due to their exceptional gas solubility. However, the influence of fluorinated functional group on N2 solvation and solubility enhancement remains unclear. Massive molecular dynamics simulations and free energy perturbation methods are conducted to investigate the N2 solubility in 11 traditional and 9 fluorinated ILs. It shows that the fluorinated IL of 1-Ethyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate ([Emim]FAP) exhibits ultrahigh solubility, 4.844 × 10-3, approximately 118 times higher than that of traditional IL 1-Ethyl-3-methylimidazolium nitrate ([Emim]NO3). Moreover, fluorinated ILs with more than 10 C-F bonds possess higher N2 solubility than others and show an exothermic nature during solvation. As the C-F bonds number in ILs decreases, the N2 solubility decreases significantly and displays the opposite endothermic behavior. To understand the ultrahigh N2 solubility in fluorinated ILs, we propose a concept of fluorine densification energy (FDE), referring to the average strength of interaction between atoms per unit volume in ILs with fluorine domains, demonstrating a linear relationship with C-F bonds. Physically, lower FDE results in lower N2-anion pair dissociation energy and higher free volume, finally enhancing the N2 solubility. Consequently, medium to long alkyl fluorine tails within a polar environment defines a distinct fluorine domain, emphasizing FDE's role in enhancing N2 solubility. Overall, these quantitative results will not only deepen the understanding of N2 solvation in ILs but may also shed light on the rational design of IL-based high-performance N2 capture and conversion technologies.

Nitrogen electroreduction to ammonia with phosphonium proton shuttles: Mass-transport vs. electrode surface chemistry effects

Nitrogen electroreduction to ammonia with phosphonium proton shuttles: Mass-transport vs. electrode surface chemistry effects

Self-enhanced localized alkalinity at the encapsulated Cu catalyst for superb electrocatalytic nitrate/nitrite reduction to NH3 in neutral electrolyte.

The electrocatalytic nitrate/nitrite reduction reaction (eNOx-RR) to ammonia (NH3) is thermodynamically more favorable than the eye-catching nitrogen (N2) electroreduction. To date, the high eNOx-RR-to-NH3 activity is limited to strong alkaline electrolytes but cannot be achieved in economic and sustainable neutral/near-neutral electrolytes. Here, we construct a copper (Cu) catalyst encapsulated inside the hydrophilic hierarchical nitrogen-doped carbon nanocages (Cu@hNCNC). During eNOx-RR, the hNCNC shell hinders the diffusion of generated OH- ions outward, thus creating a self-enhanced local high pH environment around the inside Cu nanoparticles. Consequently, the Cu@hNCNC catalyst exhibits an excellent eNOx-RR-to-NH3 activity in the neutral electrolyte, equivalent to the Cu catalyst immobilized on the outer surface of hNCNC (Cu/hNCNC) in strong alkaline electrolyte, with much better stability for the former. The optimal NH3 yield rate reaches 4.0 moles per hour per gram with a high Faradaic efficiency of 99.7%. The strong-alkalinity-free advantage facilitates the practicability of Cu@hNCNC catalyst as demonstrated in a coupled plasma-driven N2 oxidization with eNOx-RR-to-NH3.

Enhanced nitrogen electroreduction to ammonia activities on Sb2S3 electrocatalyst by sulfur defects coupled with carbon doping

Exploiting effective, robust while cheap catalysts for the nitrogen reduction reaction (NRR) is of great significance in the scalability and renewability of electrochemical NH3 synthesis. Herein, a synergetic strategy of C dopants and S vacancies was employed into Sb2S3 (marked as C-Sb2S3-x) to boost the electrochemical NRR performance. The induced effects of C dopants and S vacancies of Sb2S3 on the physical and electrochemical behaviors were throughly investigated. Experiments verify that, the content of low oxidation state in Sb species are remarkably enhanced after introducing C dopants and S vacancies, this facilitate the enhanced electric conductivity and NRR activities of C-Sb2S3-x, together with the encouraged reaction kinetics. The prepared C-Sb2S3-x delivered an optimized NH3 yield rate of 47.2 μg h−1 mg−1cat. at −0.6 V along with a high Faradaic efficiency value of 6.4 % at −0.5 V in acid, outperforming than those of Sb2S3 and most disclosed sulfid NRR electrocatalysts. Density functional theory calculations validate that, cooperation of C doping and S vacancy could achieve the elevated NH3 yield rate, Faradaic efficiency as well as competitive stability. This approach puts forward an effective strategy for transition metal compounds to be more suitable for efficient electrocatalysis.

Cooperation between single atom catalyst and support to promote nitrogen electroreduction to ammonia: A theoretical insight

The co-catalysis between single atom catalyst (SAC) and its support has recently emerged as a promising strategy to synergistically boost the catalytic activity of some complex electrochemical reactions, encompassing multiple intermediates and pathways. Herein, we utilized defective BC3 monolayer-supported SACs as a prototype to investigate the cooperative effects of SACs and their support on the catalytic performance of the nitrogen reduction reaction (NRR) for ammonia (NH3) production. The results showed that these SACs can be firmly stabilized on these defective BC3 supports with high stability against aggregation. Furthermore, co-activation of the inert N2 reactant was observed in certain embedded SACs and their neighboring B atoms on certain BC3 sheets due to the noticeable charge transfer and significant N–N bond elongation. Our high-throughput screening revealed that the Mo/DVCC and W/DVCC exhibit superior NRR catalytic performance, characterized by a low limiting potential of −0.33 and −0.43 V, respectively, which can be further increased under acid conditions based on the constant potential method. Moreover, varying NRR catalytic activities can be attributed to the differences in the valence state of active sites. Remarkably, further microkinetic modeling analysis displayed that the turnover frequency of N2–to–NH3 conversion on Mo/DVCC is as large as 1.20 × 10−3 s−1 site−1 at 700 K and 100 bar, thus guaranteeing its ultra-fast reaction rate. Our results not only suggest promising advanced electrocatalysts for NRR but also offer an effective avenue to regulate the electrocatalytic performance via the co-catalytic metal–support interactions.

Effect of Facet on Local Electron Density of Oxygen Vacancy in Catalysts for Nitrogen Electro-Reduction.

Oxygen-vacancy (Ov) engineering is an effective strategy to manipulate the electronic configuration of catalysts for electrochemical nitrogen reduction reaction (eNRR). The influence of the stable facet on the electronic configuration of Ov is widely studied, however, the effect of the reactive facet on the local electron density of Ov is unveiled. In this work, an eNRR electrode R(111)-TiO2/HGO is provided with a high proportion exposed reactive facet (111) of rutile-TiO2 (denoted as R(111)-TiO2) nanocrystals with Ov anchored in hierarchically porous graphite oxide (HGO) nanofilms. The R(111)-TiO2/HGO exhibits excellent eNRR performance with an NH3 yield rate of 20.68 µg h-1 cm-2, which is ≈20 times the control electrode with the most stable facet (110) exposed (R(110)-TiO2/HGO). The experimental data and theoretical simulations reveal that the crystal facet (111) has a positive effect on regulating the local electron density around the oxygen vacancy and the two adjacent Ti-sites, promoting the π-back-donation, minimizing the eNRR barrier, and transforming the rate determination step to *NNH→*NNHH. This work illuminates the effect of crystal facet on the performance of eNRR, and offers a novel strategy to design efficient eNRR catalysts.

Biomimetic Design of a Dynamic M-O-V Pyramid Electron Bridge for Enhanced Nitrogen Electroreduction.

Electrochemical nitrogen reduction reaction (eNRR) offers a sustainable route for ammonia synthesis; however, current electrocatalysts are limited in achieving optimal performance within narrow potential windows. Herein, inspired by the heliotropism of sunflowers, we present a biomimetic design of Ru-VOH electrocatalyst, featuring a dynamic Ru-O-V pyramid electron bridge for eNRR within a wide potential range. In situ spectroscopy and theoretical investigations unravel the fact that the electrons are donated from Ru to V at lower overpotentials and retrieved at higher overpotentials, maintaining a delicate balance between N2 activation and proton hydrogenation. Moreover, N2 adsorption and activation were found to be enhanced by the Ru-O-V moiety. The catalyst showcases an outstanding Faradaic efficiency of 51.48% at -0.2 V (vs RHE) with an NH3 yield rate exceeding 115 μg h-1 mg-1 across the range of -0.2 to -0.4 V (vs RHE), along with impressive durability of over 100 cycles. This dynamic M-O-V pyramid electron bridge is also applicable to other metals (M = Pt, Rh, and Pd).

Active MoS2-based electrode for green ammonia synthesis

Nitrogen electro-reduction under mild conditions is one promising alternative approach of the energy-consuming Haber-Bosch process for the artificial ammonia synthesis. One critical aspect to unlocking this technology is to discover the catalysts with high selectivity and efficiency. In this work, the N2-to-NH3 conversion on the functional MoS2 is fully investigated by density functional theory calculations since the layered MoS2 provides the ideal platform for the elaborating copies of the nitrogenase found in nature, wherein the functionalization is achieved via basal-adsorption, basal-substitution or edge-substitution of transition metal elements. Our results reveal that the edge-functionalization is a feasible strategy for the activity promotion; however, the basal-adsorption and basal-substitution separately suffer from the electrochemical instability and the NRR inefficiency. Specifically, MoS2 functionalized via edge W-substitution exhibits an exceptional activity. The energetically favored reaction pathway is through the distal pathway and a limiting potential is less than 0.20 V. Overall, this work escalates the rational design of the high-effective catalysts for nitrogen fixation and provides the explanation why the predicated catalyst have a good performance, paving the guidance for the experiments.

Regulation of cerium species in Keggin structure of phosphotungstic acid for efficient nitrogen electroreduction to ammonia

As a sustainable and economical strategy, electrochemical nitrogen reduction reaction (eNRR) is a promising alternative of energy-intensive Haber-Bosch process to produce ammonia. Fabricating efficient catalysts for eNRR is still challenging due to the bottleneck of insufficient activity and low electron selectivity. Herein, phosphotungstic acid (PTA) as substrate to anchor cerium species on the 4-fold hollow site was prepared, which reaches high ammonia yield rates of 42 μg h−1 mgcat−1 and Faradaic efficiencies of 9.2 % at −0.6 V versus reversible hydrogen electrode. Experiments and theoretical calculations reveal that the introduction of Ce species could significantly improve the electronic density of adjacent exposed W atoms, further boosting the effective adsorption and activation of N2 to form active *N2. Finally, the designed Ce-PTA catalysts show high electrocatalytic activity of N2 reduction into ammonia. This work highlights the important role of using PTA as substrate to prepare stable supported metal species for heterogeneous electrocatalysis.

Tailor-made yolk-shell nanocomposites of star-shape Au and porous organic polymer for nitrogen electroreduction to ammonia

Electrocatalytic nitrogen (N2) reduction reaction (NRR) is an energy-saving approach to synthesize ammonia (NH3), which significantly depends on the development of high-efficiency electrocatalysts. Inspired by the catalytic microenvironment of enzymes, a series of yolk-shell nanostructures of monodispersed Au nanostars within porous organic polymers (POPs) have been successfully prepared via a self-sacrificing template strategy. The obtained yolk-shell nanocomposites have highly active Au nanostar cores and permeable POP shells for ambient electrocatalytic NRR to NH3. The hydrophobic properties of yolk-shell nanoreactors can be tailored accurately by engineering the POP shells at an atomic level, which greatly improves the N2 fixation performance by inhibiting the hydrogen evolution reaction, resulting in the unprecedented NH3 yield rate (∼109.1 μg h−1 mgcat.−1) and Faradaic efficiency (∼68.3 %). This work pioneers an effective strategy to construct tailor-made electrocatalysts for the N2-to-NH3 fixation.

Surface modification of CeO2−x nanorods with Sn doping for enhanced nitrogen electroreduction

While the electrochemical nitrogen reduction reaction (NRR) represents a prospective blueprint for environmentally renewable ammonia generation, it has yet to overcome the limitations of weak activity and inferior selectivity. In this regard, surface modification tactic was constructed to markedly enhance the activity and selectivity via introducing Sn atoms into the surface of defective cerium oxide (denoted as Sn-CeO2−x) as the active and robust electrocatalyst for NRR under benign environment. The introduction of Sn atoms in CeO2−x can not only inhibit the HER activity of the catalyst but also modulate the electronic structure of ceria and optimize N-Ce interaction, thus enhancing NRR activity and selectivity. Outperforming all previous CeO2-based NRR catalysts, this catalyst has demonstrated an ammonia yield rate of 41.1 μg mgcat−1 h−1 and an exceptional Faradic efficiency of 35.3%. This work presents a viable approach for the development of advanced NRR electrocatalysts.

Enhanced nitrogen electroreduction performance by the reorganization of local coordination environment of supported single atom on N(O)-dual-doped graphene

Enhanced nitrogen electroreduction performance by the reorganization of local coordination environment of supported single atom on N(O)-dual-doped graphene

Hydrophobicity Tailoring of Ferric Covalent Organic Framework/MXene Nanosheets for High-Efficiency Nitrogen Electroreduction to Ammonia.

Electrocatalytic nitrogen reduction reaction (NRR) represents a promising sustainable approach for NH3 synthesis. However, the poor NRR performance of electrocatalysts is a great challenge at this stage, mainly owing to their low activity and the competitive hydrogen evolution reaction (HER). Herein, 2D ferric covalent organic framework/MXene (COF-Fe/MXene) nanosheets with controllable hydrophobic behaviors are successfully prepared via a multiple-in-one synthetic strategy. The boosting hydrophobicity of COF-Fe/MXene can effectively repel water molecules to inhibit the HER for enhanced NRR performances. By virtue of the ultrathin nanostructure, well-defined single Fe sites, nitrogen enrichment effect, and high hydrophobicity, the 1H,1H,2H,2H-perfluorodecanethiol modified COF-Fe/MXene hybrid shows a NH3 yield of 41.8µg h-1 mgcat. -1 and a Faradaic efficiency of 43.1% at -0.5V versus RHE in a 0.1m Na2 SO4 water solution, which are vastly superior to the known Fe-based catalysts and even to the noble metal catalysts. This work provides a universal strategy to design and synthesis of non-precious metal electrocatalysts for high-efficiency N2 reduction to NH3 .

Fluorine‐Stabilized Defective Black Phosphorene as a Lithium‐Like Catalyst for Boosting Nitrogen Electroreduction to Ammonia

AbstractElectrocatalytic N2 reduction reaction (NRR) is recognized as a zero‐carbon emission method for NH3 synthesis. However, to date, this technology still suffers from low yield and low selectivity associated with the catalyst. Herein, inspired by the activation of N2 by lithium metal, a highly reactive defective black phosphorene (D−BPene) is proposed as a lithium‐like catalyst for boosting electrochemical N2 activation. Correspondingly, we also report a strategy for producing environmentally stable D−BPene by simultaneously constructing defects and fluorination protection based on topochemical reactions. Reliable performance evaluations show that the fluorine‐stabilized D−BPene can induce a high NH3 yield rate of ≈70 μg h−1 mgcat.−1 and a high Faradaic efficiency of ≈26 % at −0.5 V vs. RHE in an aqueous electrolyte. This work not only exemplifies the first stable preparation and practical application of D−BPene, but also brings a new design idea for NRR catalysts.

Fluorine-Stabilized Defective Black Phosphorene as a Lithium-Like Catalyst for Boosting Nitrogen Electroreduction to Ammonia.

Electrocatalytic N2 reduction reaction (NRR) is recognized as a zero-carbon emission method for NH3 synthesis. However, to date, this technology still suffers from low yield and low selectivity associated with the catalyst. Herein, inspired by the activation of N2 by lithium metal, a highly reactive defective black phosphorene (D-BPene ) is proposed as a lithium-like catalyst for boosting electrochemical N2 activation. Correspondingly, we also report a strategy for producing environmentally stable D-BPene by simultaneously constructing defects and fluorination protection based on topochemical reactions. Reliable performance evaluations show that the fluorine-stabilized D-BPene can induce a high NH3 yield rate of ≈70 μg h-1 mgcat. -1 and a high Faradaic efficiency of ≈26 % at -0.5 V vs. RHE in an aqueous electrolyte. This work not only exemplifies the first stable preparation and practical application of D-BPene , but also brings a new design idea for NRR catalysts.

Boosting charge-transfer in tuned Au nanoparticles on defect-rich TiO2 nanosheets for enhancing nitrogen electroreduction to ammonia production

The electrocatalytic nitrogen reduction reaction (eNRR) to ammonia (NH3) has been recognized as an effective, carbon–neutral, and great-potential strategy for ammonia production. However, the conversion efficiency and selectivity of eNRR still face significant challenges due to the slow transfer kinetics and lack of effective N2 adsorption and activation sites in this process. Herein, we designed and fabricated defect-rich TiO2 nanosheets furnished with oxygen vacancies (OVs) and Au nanoparticles (Au/TiO2-x) as the electrocatalyst for efficient N2-fixing. The experimental results demonstrate that OVs act as active sites, which enable efficient chemisorption and activation of N2 molecules. The Au nanoparticles loaded on the OVs-rich TiO2 nanosheets not only accelerate charge transfer but also change the local electronic structure, thus enhancing N2 adsorption and activation. In this work, the optimal Au/TiO2-x electrocatalyst displays a considerable NH3 yield activity of 12.5 μg h−1 mgcat.-1 and a faradaic efficiency (FE) of 10.2 % at −0.40 V vs reversible hydrogen electrode (RHE). More importantly, the Au/TiO2-x exhibits a stable N2-fixing activity in cycling and it persists even after 80 h of consecutive electrolysis. Density functional theory (DFT) calculations reveal that the OVs serve as the active sites in TiO2, while Au nanoparticles are crucial for improving N2 chemisorption and lowering the reaction energy barrier by facilitating the charge transfer for eNRR with a distal hydrogenation pathway. This research offers a rational catalytic site design for modulating charge transfer of active sites on metal-supported defective catalysts to boost N2 electroreduction to NH3.