Cu-Bi Bimetallic Sulfides Loaded on Two-Dimensional Ti3C2Tx MXene for Efficient Electrocatalytic Nitrogen Reduction under Ambient Conditions.

In this paper, Ti3C2Tx MXene/Cu-Bi bimetallic sulfide (Ti3C2Tx/BiCuS2.5) composites were prepared by a simple in situ deposition method for electrocatalytic nitrogen reduction reaction (eNRR). Compared to Ti3C2Tx/Bi2S3 and Ti3C2Tx/CuS, the eNRR performance of Ti3C2Tx/BiCuS2.5 is significantly improved. The results show that Ti3C2Tx/BiCuS2.5 exhibits a NH3 yield of 62.57 µg h-1 mg-1cat. in 0.1 M Na2SO4 at -0.6 V vs reversible hydrogen electrode, and the Faradaic efficiency (FE) reaches 67.69%, which is better than that of Ti3C2Tx/CuS (NH3 yield: 52.26 µg h-1 mg-1cat., FE: 34.15%) and Ti3C2Tx/Bi2S3 (NH3 yield: 54.04 µg h-1 mg-1cat., FE: 37.38%). According to density functional theory calculations, the eNRR at the Ti3C2Tx/BiCuS2.5 surface is the alternating pathway. The 1H NMR experiment of 15N proves that the N of NH3 generated in the experiment originates from N2 passed during the experiment.

A Novel Bubble-based Microreactor for Enhanced Mass Transfer Dynamics toward Efficient Electrocatalytic Nitrogen Reduction.

Electrocatalytic nitrogen reduction reaction (eNRR) is a promising method for sustainable ammonia production. Although the majority of studies on the eNRR are devoted to developing efficient electrocatalysts, it is critical to study the influence of mass transfer because of the poor N2 transfer efficiency. Herein, a novel bubble-based microreactor (BBMR) is proposed that efficiently promotes the mass transfer behavior during the eNRR using microfluidic strategies. The BBMR possesses abundant triphasic interfaces and provides spatial confinement and accurate potential control, ensuring rapid mass transfer dynamics and improved eNRR performance, as confirmed by experimental and simulation studies. The ammonia yield of the reaction over Ag nanoparticles can be enhanced to 31.35 µg h-1 mgcat. -1, which is twice that of the H-cell. Excellent improvements are also achieved using Ru/C and Fe/g-CN catalysts, with 5.0 and 8.5 times increase in ammonia yield, respectively. This work further demonstrates the significant effect of mass transfer on the eNRR performance and provides an effective strategy for process enhancement through electrode design.

Coordination Engineering of Heteronuclear Fe-Mo Dual-Atom Catalyst for Promoted Electrocatalytic Nitrogen Fixation: A DFT Study.

Developing efficient nanostructured electrocatalysts for N2 reduction to NH3 under mild conditions remains a major challenge. The Fe-Mo cofactor serves as the archetypal active site in nitrogenase. Inspired by nitrogenase, we designed a series of heteronuclear dual-atom catalysts (DACs) labeled as FeMoN6-a Xa (a=1, 2, 3; X=B, C, O, S) anchored on the pore of g-C3 N4 to probe the impact of coordination on FeMo-catalyzed nitrogen fixation. The stability, reaction paths, activity, and selectivity of 12 different FeMoN6-a Xa DACs have been systematically studied using density functional theory. Of these, four DACs (FeMoN5 B1 , FeMoN5 O1 , FeMoN4 O2 , and FeMoN3 C3 ) displayed promising nitrogen reduction reaction (NRR) performance. Notably, FeMoN5 O1 stands out with an ultralow limiting potential of -0.11 V and high selectivity. Analysis of the density of states and charge/spin changes shows FeMoN5 O1 's high activity arises from optimal N2 binding on Fe initially and synergy of the FeMo dimer enabling protonation in NRR. This work contributes to the advancement of rational design for efficient NRR catalysts by regulating atomic coordination environments.

First-Principles Study of Bimetallic Pairs Embedded on Graphene Co-Doped with N and O for N2 Electroreduction.

The electrocatalytic nitrogen reduction reaction (NRR) is considered a viable alternative to the Haber-Bosch process for ammonia synthesis, and the design of highly active and selective catalysts is crucial for the industrialization of the NRR. Dual-atom catalysts (DACs) with dual active sites offer flexible active sites and synergistic effects between atoms, providing more possibilities for the tuning of catalytic performance. In this study, we designed 48 graphene-based DACs with N4O2 coordination (MM'@N4O2-G) using density functional theory. Through a series of screening strategies, we explored the reaction mechanisms of the NRR for eight catalysts in depth and revealed the "acceptance-donation" mechanism between the active sites and the N2 molecules through electronic structure analysis. The study found that the limiting potential of the catalysts exhibited a volcano-shaped relationship with the d-band center of the active sites, indicating that the synergistic effect between the bimetallic components can regulate the d-band center position of the active metal M, thereby controlling the reaction activity. Furthermore, we investigated the selectivity of the eight DACs and identified five potential NRR catalysts. Among them, MoCo@N4O2-G showed the best NRR performance, with a limiting potential of -0.20 V. This study provides theoretical insights for the design and development of efficient NRR electrocatalysts.

Plasmonic-Promoted Interatomic Hot Carriers Regulation Enhanced Electrocatalytic Nitrogen Reduction Reaction.

Utilizing hot carriers for efficient plasmonic-mediated chemical reactions (PMCRs) to convert solar energy into secondary energy is one of the most feasible solutions to the global environmental and energy crisis. Finding a plasmonic heterogeneous nanostructure with a more efficient and reasonable hot carrier transport path without affecting the intrinsic plasmonic properties is still a major challenge that urgently needs to be solved in this field. Herein, the mechanism by which plasmonic-promoted interatomic hot electron redistribution on the surface of Au3Cu alloy nanoparticles promotes the electrocatalytic nitrogen reduction reaction (ENRR) is successfully clarified. The localized surface plasmon resonance (LSPR) effect can boost the transfer of plasmonic hot electrons from Au atoms to Cu atoms, trigger the interatomic electron regulation of Au3Cu alloy nanoparticles, enhance the desorption of ammonia molecules, and increase the ammonia yield by approximately 93.9%. This work provides an important reference for rationally designing and utilizing the LSPR effect to efficiently regulate the distribution and mechanism of plasmonic hot carriers on the surface of heterogeneous alloy nanostructures.

Jahn-Teller Distortions Induced by in situ Li Migration in λ-MnO2 for Boosting Electrocatalytic Nitrogen Fixation.

Lithium-mediated electrochemical nitrogen reduction reaction (Li-NRR) completely eschews the competitive hydrogen evolution reaction (HER) occurred in aqueous system, whereas the continuous deposition of lithium readily blocks the active sites and further reduces the reaction kinetics. Herein, we propose an innovative in situ Li migration strategy to realize that Li substitutes Mn sites in λ-MnO2 instead of evolving into the dead Li. Comprehensive characterizations corroborate that the intercalation of Li+ at high voltage breaks the structural integrity of MnO6 octahedron and further triggers unique Jahn-Teller distortions, which promotes the spin state regulation of Mn sites to generate the ameliorative eg orbital configuration and accelerates N≡N bond cleavage via eg -σ and eg -π* interaction. To this end, the resulted cationic disordered LiMnO4 delivers the recorded highest NH3 yield rate of 220 µg h-1 cm-2 and a Faradaic efficiency (FE) 83.80 % in organic electrolyte.

Controllable Exfoliation of MOF-Derived Van Der Waals Superstructure into Ultrathin 2D B/N Co-Doped Porous Carbon Nanosheets: A Superior Catalyst for Ambient Ammonia Electrosynthesis.

The electrocatalytic nitrogen reduction reaction (NRR) to synthesize NH3 under ambient conditions is a promising alternative route to the conventional Haber-Bosch process, but it is still a great challenge to develop electrocatalysts' high Faraday efficiency and ammonia yield. Herein, a facile and efficient exfoliation strategy to synthesize ultrathin 2D boron and nitrogen co-doped porous carbon nanosheets (B/NC NS) via a metal-organic framework (MOF)-derived van der Waals superstructure, is reported. The results of experiments and theoretical calculations show that the doping of boron and nitrogen can modulate the electronic structure of the adjacent carbon atoms; which thus, promotes the competitive adsorption of nitrogen and reduces the energy required for ammonia synthesis. The B/NC NS exhibits excellent catalytic performance and stability in electrocatalytic NRR, with a yield rate of 153.4 µg·h-1 ·mg-1 cat and a Faraday efficiency of 33.1%, which is better than most of the reported NRR electrocatalysts. The ammonia yield of B/NC NS can maintain 92.7% of the initial NRR activity after 48 h stability test. The authors' controllable exfoliation strategy using MOF-derived van der Waals superstructure can provide a new insight for the synthesis of other 2D materials.

Role of Peripheral Coordination Boron in Electrocatalytic Nitrogen Reduction over N-Doped Graphene-Supported Single-Atom Catalysts.

In this work, we investigate the effect of peripheral B doping on the electrocatalytic nitrogen reduction reaction (NRR) performance of N-doped graphene-supported single-metal atoms using density functional theory (DFT) calculations. Our results showed that the peripheral coordination of B atoms could improve the stability of the single-atom catalysts (SACs) and weaken the binding of nitrogen to the central atom. Interestingly, it was found that there was a linear correlation between the change in the magnetic moment (µ) of single-metal atoms and the change in the limiting potential (UL) of the optimum NRR pathway before and after B doping. It was also found that the introduction of the B atom suppressed the hydrogen evolution reaction, thereby enhancing the NRR selectivity of the SACs. This work provides useful insights into the design of efficient SACs for electrocatalytic NRR.

Single-Atom Gold Isolated Onto Nanoporous MoSe2 for Boosting Electrochemical Nitrogen Reduction.

The electrocatalytic nitrogen reduction reaction (NRR) provides a promising strategy to convert the abundant but inert N2 into NH3 using renewable energy. Herein, single-atom Au isolated onto bicontinous nanoporous MoSe2 (np-MoSe2 ) is designed as an electrocatalyst for achieving highly efficient NRR catalysis, which exhibits a high Faradaic efficiency (FE) of 37.82% and an NH3 production rate of 30.83 µg h-1 mg-1 at -0.3 V versus a reversible hydrogen electrode (RHE) in 0.1 m Na2 SO4 under ambient conditions. Experimental and theoretical investigations reveal that the introduction of single Au atoms onto np-MoSe2 optimizes the adsorption of NRR intermediates while suppressing the competing HER, thus providing an energetic-favorable process for enhancing the catalytic selectivity toward electrochemical N2 reduction into NH3 .

PdFe Single-Atom Alloy Metallene for N2 Electroreduction.

Single-atom alloys hold great promise for electrocatalytic nitrogen reduction reaction (NRR), while the comprehensive experimental/theoretical investigations of SAAs for the NRR are still missing. Herein, PdFe1 single-atom alloy metallene, in which the Fe single atoms are confined on a Pd metallene support, is first developed as an effective and robust NRR electrocatalyst, delivering exceptional NRR performance with an NH3 yield of 111.9 µg h-1 mg-1 , a Faradaic efficiency of 37.8 % at -0.2 V (RHE), as well as a long-term stability for 100 h electrolysis. In-depth mechanistic investigations by theoretical computations and operando X-ray absorption/Raman spectroscopy indentify Pd-coordinated Fe single atoms as active centers to enable efficient N2 activation via N2 -to-Fe σ-donation, reduced protonation energy barriers, suppressed hydrogen evolution and excellent thermodynamic stability, thus accounting for the high activity, selectivity and stability of PdFe1 for the NRR.

Synergistic Enhancement of Electrocatalytic Nitrogen Reduction Over Boron Nitride Quantum Dots Decorated Nb2 CTx -MXene.

Electrochemical N2 fixation represents a promising strategy toward sustainable NH3 synthesis, whereas the rational design of high-performance catalysts for the nitrogen reduction reaction (NRR) is urgently required but remains challenging. Herein, a novel hexagonal BN quantum dots (BNQDs) decorated Nb2 CTx -MXene (BNQDs@Nb2 CTx ) is explored as an efficient NRR catalyst. BNQDs@Nb2 CTx presents the optimum NRR activity with an NH3 yield rate of 66.3 µg h-1 mg-1 (-0.4 V) and a Faradaic efficiency of 16.7% (-0.3 V), outperforming most of the state-of-the-art NRR catalysts, together with an excellent stability. Theoretical calculations revealed that the synergistic interplay of BNQDs and Nb2 CTx enabled the creation of unique interfacial B sites serving as NRR catalytic centers capable of enhancing the N2 activation, lowering the reaction energy barrier and impeding the H2 evolution.

Exploration and Investigation of Periodic Elements for Electrocatalytic Nitrogen Reduction.

High demand for green ecosystems has urged the human community to reconsider and revamp the traditional way of synthesis of several compounds. Ammonia (NH3 ) is one such compound whose applications have been extended from fertilizers to explosives and is still being synthesized using the high energy inhaling Haber-Bosch process. Carbon free electrocatalytic nitrogen reduction reaction (NRR) is considered as a potential replacement for the Haber-Bosch method. However, it has few limitations such as low N2 adsorption, selectivity (competitive HER reactions), low yield rate etc. Since it is at the early stage, tremendous efforts have been devoted in understanding the reaction mechanism and screening of the electrocatalysts and electrolytes. In this review, the electrocatalysts are classified based on the periodic table with heat maps of Faraday efficiency and yield rate of NH3 in NRR and their electrocatalytic properties toward NRR are discussed. Also, the activity of each element is discussed and short tables and concise graphs are provided to enable the researchers to understand recent progress on each element. At the end, a perspective is provided on countering the current challenges in NRR. This review may act as handbook for basic NRR understandings, recent progress in NRR, and the design and development of advanced electrocatalysts and systems.

Boosting the Faraday Efficiency of Electrochemical Ammonia Synthesis via the Strain Effect Induced by Interfacial Hybrid Formation between BN and Carbon Nanotubes.

The electrochemical nitrogen reduction reaction (eNRR) is a highly promising alternative to the Haber-Bosch (H-B) process, but its commercial development is limited by the high bond energy of N2 molecules and the presence of the competitive hydrogen evolution reaction (HER). Here, a metal-free composite electrocatalyst of boron nitride (h-BNNs) and carbon nanotubes (CNTs) was explored through the interfacial hybridization of h-BNNs and CNTs, which showed a highly improved eNRR Faraday efficiency (FE) of 63.9% and an NH3 yield rate of 36.5 µg h-1 mgcat.-1 at -0.691 V (vs RHE). New chemical bonds of C-B and C-N were observed, indicating a strong interaction between CNTs and h-BNNs. According to the Raman spectra and the optimized model of h-BNNs/CNTs, an obvious strain effect between h-BNNs and CNTs was supposed to play a significant role in the highly improved FE, compared with the FE of h-BNNs alone (4.7%). Density functional theory (DFT) calculations further showed that h-BNNs/CNTs had lower energy barriers in eNRR, giving them higher N2 to NH3 selectivity, while h-BNNs have lower energy barriers in the HER. This work shows the important role of the strain effect in boosting the selectivity in the eNRR process.

Machine learning-driven shortening the screening process towards high-performance nitrogen reduction reaction electrocatalysts with four-step screening strategy.

The urgent need to prepare clean energy by environmentally friendly and efficient methods, which has led to widespread attention on electrocatalytic nitrogen reduction reaction (NRR) for ammonia production. At present, single atom catalytic nitrogen reduction has become the earliest promising method for industrial production due to its high atomic utilization rate, high selectivity, high controllability, and high stability. However, how to quickly screen catalysts with high catalytic efficiency and selectivity in single-atom catalysts (SACs) remains a challenge. Herein, the 29 SACs are constructed from C6N2 nanosheets doped with transition metals (TM@C6N2), which are analyzed for stability, adsorption performance, NRR catalytic activity, electronic properties, and competitiveness using first-principles calculations. The results show that Mo@C6N2 and Re@C6N2 exhibit the most outstanding catalytic performances, with limiting potentials (UL) of -0.29 and -0.31 V, respectively, in the solvent model. Machine learning is used to derive descriptors from the intrinsic features to predict the free energy changes for the potential-determining step. The importance of features is calculated, with the first ionisation energy (IE1) being the most significant influencing factor. Based on the guidance of machine learning and considering that IE1 is related to the ability of metal atoms to donate electrons, a four-step screening strategy using the Integrated Crystal Orbital Hamilton Populations (ICOHP) to screen catalysts instead of the traditional five-step screening not only improves the screening efficiency but also obtains completely consistent screening results. This work presents a new approach to predicting the catalytic performance of SACs and provides new insights into the influence of intrinsic properties on catalytic activity.

Laser regulated mixed-phase TiO2 for electrochemical overall nitrogen fixation.

Traditional oxide electrocatalytic materials encounter significant challenges associated with sluggish reaction kinetics and formidable energy barriers for NH intermediates formation in electrocatalytic nitrogen fixation. The implementation of phase control emerges as an effective strategy to address these challenges. Herein, leveraging the energy localization of laser, this work achieved precise phase control of TiO2. In the optimized material system, the rutile phase TiO2 facilitates nitrogen adsorption, while the anatase phase TiO2 provides proton sources and active oxygen species. The synergistic effect of the two phases effectively enhances the electrocatalytic activity for nitrogen reduction and oxidation, with an ammonia yield reaching âˆ¼22.3 µg h-1 cm-2 and a nitrate yield reaching âˆ¼60.9 µg h-1 cm-2. Furthermore, a coupled dual-electrode system with mixed-phase titanium dioxide as both the anode and cathode successfully achieved a breakthrough in electrochemical overall nitrogen fixation. This laser precision control strategy for manipulating phase sites lays the groundwork for designing efficient catalysts for energy conversion and even energy storage nanomaterials.

Rational design of bimetallic MBene for efficient electrocatalytic nitrogen reduction.

Electrocatalytic nitrogen reduction reaction (NRR) is one of the most promising approaches to achieving green and efficient NH3 production. However, the designs of efficient NRR catalysts with high activity and selectivity still are severely hampered by inherent linear scaling relations among the adsorption energies of NRR intermediates. Herein, the properties of ten M3B4 type MBenes have been initially investigated for efficient N2 activation and reduction to NH3via first-principles calculations. We highlight that Cr3B4 MBene possesses remarkable NRR activity with a record-low limiting potential (-0.13 V). Then, this work proposes descriptor-based design principles that can effectively evaluate the catalytic activity of MBenes, which have been further employed to design bimetallic M2M'B4 MBenes. As a result, 5 promising candidates including Ti2YB4, V2YB4, V2MoB4, Nb2YB4, and Nb2CrB4 with excellent NRR performance have been extracted from 20 bimetallic MBenes. Further analysis illuminates that constructing bimetallic MBenes can selectively tune the adsorption strength of NHNH2** and NH2NH2**, and break the linear scaling relations between their adsorption energies, rendering them ideal for NRR. This work not only pioneers the application of MBenes as efficient NRR catalysts but also proposes rational design principles for boosting their catalytic performance.

Iron Monomers or Trimers on Nitrogen-Doped Carbon: Which Is Better for the Electrocatalytic Nitrogen Reduction Reaction?

The electrocatalytic nitrogen reduction reaction (NRR) presents an alternative method for the Haber-Bosch process, and single-atom catalysts (SACs) to achieve efficient NRR have attracted considerable attention in the past decades. However, whether SACs are more suitable for NRR compared to atomic-cluster catalysts (ACCs) remains to be studied. Herein, we have successfully synthesized both the Fe monomers (Fe1) and trimers (Fe3) on nitrogen-doped carbon catalysts. Both the experiments and DFT calculations indicate that compared to the end-on adsorption of N2 on Fe1 catalysts, N2 activation is enhanced via the side-on adsorption on Fe3 catalysts, and the reaction follows the enzymatic pathway with a reduced free energy barrier for NRR. As a result, the Fe3 catalysts achieved better NRR performance (NH3 yield rate of 27.89 µg h-1 mg-1cat. and Faradaic efficiency of 45.13%) than Fe1 catalysts (10.98 µg h-1 mg-1cat. and 20.98%). Therefore, our research presents guidance to prepare more efficient NRR catalysts.

Surface Electronic Properties-Driven Electrocatalytic Nitrogen Reduction on Metal-Conjugated Porphyrin 2D-MOFs.

Two-dimensional (2D) metal organic framework (MOF) or metalloporphyrin nanosheets with a stable metal-N4 complex unit present the metal as a single-atom catalyst dispersed in the 2D porphyrin framework. First-principles calculations on the 3d-transition metals in M-TCPP are investigated in this study for their surface-dependent electronic properties including work function and d-band center. Crystal orbital Hamiltonian population (-pCOHP) analysis highlights a higher contribution of the bonding state in the M-N bond and antibonding state in the N-N bond to be essential for N-N bond activation. A linear relationship between ΔGmax and surface electronic properties, N-N bond strength, and Bader charge has been found to influence the rate-determining potential for nitrogen reduction reaction (NRR) in M-TCPP MOFs. 2D Ti-TCPP MOF, with a kinetic energy barrier of 1.43 eV in the final protonation step of enzymatic NRR, shows exclusive NRR selectivity over competing hydrogen reduction (HER) and nitrogenous compounds (NO and NO2). Thus, Ti-TCPP MOF with an NRR limiting potential of -0.35 V in water solvent is proposed as an attractive candidate for electrocatalytic NRR.

Oxygen vacancy modulation in interfacial engineering Fe3O4 over carbon nanofiber boosting ambient electrocatalytic N2 reduction.

The oxygen vacancy modulation of interface-engineered Fe3O4 nanograins over carbon nanofiber (Fe@CNF) was achieved to improve electrocatalytic nitrogen reduction reaction (NRR) activity and stability via facile electrospinning and tuning thermal procedure. The optimal catalyst calcined at 800 ℃ (Fe@CNF-800) was endowed with abundant nanograin boundaries and optimized oxygen vacancy (Vo) concentration of iron oxides, thereby affording 37.1 µg h-1 mgcat.-1 (-0.2 V vs. reversible hydrogen electrode (RHE)) NH3 yield and rational Faraday efficiency (10.2%), with 13.6 times atomic activity enhancement compared to of that commercial Fe3O4. The interfacial effect of assembled nanograins in particles correlated with the formation of Vo and more intrinsic active sites, which is conducive to the trapping and activation of nitrogen (N2). The in-situ X-ray photoelectron spectroscopy (XPS) measurement revealed the real consumption of adsorbed oxygen when introducing N2 by the trapping effect of Vo. Density-Functional-Theory (DFT) calculation validates the promotive hydrogenation effect and elimination of hydrogen intermediate (H*) interacted with N2 transferring toward oxygen of the support. The optimal catalyst shows a lasting NRR activity at least 90 h, outperforming most reported Fe-based NRR catalysts.

Basal Plane-Activated Boron-Doped MoS2 Nanosheets for Efficient Electrochemical Ammonia Synthesis.

Under the dual pressure of energy crisis and environmental pollution, ammonia (NH3 ) is an indispensable chemical product in the global economy. The electrocatalytic synthesis of NH3 directly from nitrogen and water using renewable electricity has become one of the most attractive and important topics. Basal plane-activated boron-doped MoS2 nanosheets (B-MoS2 ) as a non-noble metal catalyst with excellent performance for N2 electroreduction are synthesized by a facile one-step hydrothermal method. In 0.1 m Na2 SO4 solution, MoS2 nanosheets doped with 300 mg boric acid (B-MoS2 -300) give rise to a good ammonia yield rate of 75.77 µg h-1 mg-1 cat. at -0.75 V vs. RHE, and an excellent Faradaic efficiency of 40.11 % at -0.60 V vs. RHE. In addition, the B-MoS2 -300 nanosheets show good selectivity and chemical stability, and no hydrazine (N2 H4 ) by-product is generated during the reaction. 15 N isotopic labeling confirms that nitrogen in produced ammonia originates from N2 in the electrolyte. On the one hand, the high conductivity of MoS2 guarantees guarantees a high electron transfer rate from nitrogen to ammonia; on the other hand, the successful incorporation of heteroatom B enlarges the interlayer spacing of MoS2 , and the B atom can act as an active site for basal plane activation, providing more active sites for the nitrogen reduction reaction (NRR). Density functional theory calculations show that the doping of B activates the base plane of 1T-MoS2 , which makes the adsorption of N2 on the base plane easier and promotes the NRR.