Single Metal Site Research Articles

Selective nitrogen reduction to ammonia on iron porphyrin-based single-site metal–organic frameworks

Constructing efficient catalysts for N2 reduction into value added ammonia under ambient conditions is a considerable challenge.

Carbon support tuned electrocatalytic activity of a single-site metal-organic framework toward the oxygen reduction reaction.

Metal–organic frameworks (MOFs) possess fantastic features such as structural diversity, tunable accessible pores and atomically dispersed active sites, holding tremendous potential as highly versatile platforms for fabricating single-site catalysts. The electrocatalytic activity of single-site MOFs can be improved and tuned via several approaches; however, the exploitation of different carbon supports to modulate the nature of single active sites in MOFs for electrocatalysis has not been reported. Here, we find that the electrocatalytic activity of single-site MOFs toward the oxygen reduction reaction (ORR) can be tuned by using carbon nanomaterials, i.e., carbon nanotubes and graphene, as supports through MOF–support interactions in the manner of geometric and electronic effects. The introduction of MOF–support interactions not only greatly improves the electrocatalytic performance of MOFs toward the ORR in terms of onset and half-wave potentials and current density, but also alters the reaction pathway of the ORR. This finding provides a new horizon for the design and synthesis of single-site MOFs for electrocatalysis.

Single Metal Site and Versatile Transfer Channel Merged into Covalent Organic Frameworks Facilitate High-Performance Li-CO2 Batteries

The sluggish kinetics and unclear mechanism have significantly hindered the development of Li-CO2 batteries. Here, a Li-CO2 battery cathode catalyst based on a porphyrin-based covalent organic framework (TTCOF-Mn) with single metal sites is reported to reveal intrinsic catalytic sites of aprotic CO2 conversion from the molecular level. The battery with TTCOF-Mn exhibits a low overpotential of 1.07 V at 100 mA/g as well as excellent stability at 300 mA/g, which is one of the best Li-CO2 battery cathode catalysts to date. The unique features of TTCOF-Mn including uniform single-Mn(II)-sites, fast Li+ transfer pathways, and high electron transfer efficiency contribute to effective CO2 reduction and Li2CO3 decomposition in the Li-CO2 system. Density functional theory calculations reveal that different metalloporphyrin sites lead to different reaction pathways. The single-Mn(II) sites in TTCOF-Mn can activate CO2 and achieve an efficient four-electron CO2 conversion pathway. It is the first example to reveal the catalytic active sites and clear reaction pathways in aprotic Li-CO2 batteries.

Heterogeneously Catalysed Hydroamination

AbstractThe direct addition of amines to alkynes and olefins is an elegant approach for C−N bond formation in contrast to other conventional synthetic organic methods that afford higher substituted amines; comprising essential organo‐nitrogen compounds which are the scaffolds present in important N‐heterocycles. Heterogeneous catalyzed direct amination is presented in this Review, along with the advantages, the structure‐activity relationship of applied solid acids, functionalized nanomaterials and heterogeneous single metal site catalysts that play a pivotal role towards tuning the formation of branched and linear amines.

Chemical Vapor Deposition for Atomically Dispersed and Nitrogen Coordinated Single Metal Site Catalysts

Atomically dispersed and nitrogen coordinated single metal sites (M-N-C, M=Fe, Co, Ni, Mn) are the popular platinum group-metal (PGM)-free catalysts for many electrochemical reactions. Traditional wet-chemistry catalyst synthesis often requires complex procedures with unsatisfied reproducibility and scalability. Here, we report a facile chemical vapor deposition (CVD) strategy to synthesize the promising M-N-C catalysts. The deposition of gaseous 2-methylimidazole onto M-doped ZnO substrates, followed by an in situ thermal activation, effectively generated single metal sites well dispersed into porous carbon. In particular, an optimal CVD-derived Fe-N-C catalyst exclusively contains atomically dispersed FeN4 sites with increased Fe loading relative to other catalysts from wet-chemistry synthesis. The catalyst exhibited outstanding oxygen-reduction activity in acidic electrolytes, which was further studied in proton-exchange membrane fuel cells with encouraging performance.

Chemical Vapor Deposition for Atomically Dispersed and Nitrogen Coordinated Single Metal Site Catalysts

AbstractAtomically dispersed and nitrogen coordinated single metal sites (M‐N‐C, M=Fe, Co, Ni, Mn) are the popular platinum group‐metal (PGM)‐free catalysts for many electrochemical reactions. Traditional wet‐chemistry catalyst synthesis often requires complex procedures with unsatisfied reproducibility and scalability. Here, we report a facile chemical vapor deposition (CVD) strategy to synthesize the promising M‐N‐C catalysts. The deposition of gaseous 2‐methylimidazole onto M‐doped ZnO substrates, followed by an in situ thermal activation, effectively generated single metal sites well dispersed into porous carbon. In particular, an optimal CVD‐derived Fe‐N‐C catalyst exclusively contains atomically dispersed FeN4 sites with increased Fe loading relative to other catalysts from wet‐chemistry synthesis. The catalyst exhibited outstanding oxygen‐reduction activity in acidic electrolytes, which was further studied in proton‐exchange membrane fuel cells with encouraging performance.

Negative Pressure Pyrolysis Induced Highly Accessible Single Sites Dispersed on 3D Graphene Frameworks for Enhanced Oxygen Reduction.

Herein, we report a negative pressure pyrolysis to access dense single metal sites (Co, Fe, Ni etc.) with high accessibility dispersed on three-dimensional (3D) graphene frameworks (GFs), during which the differential pressure between inside and outside of metal-organic frameworks (MOFs) promotes the cleavage of the derived carbon layers and gradual expansion of mesopores. In situ transmission electron microscopy and Brunauer-Emmett-Teller tests reveal that the formed 3D GFs possess an enhanced mesoporosity and external surface area, which greatly favor the mass transport and utilization of metal sites. This contributes to an excellent oxygen reduction reaction (ORR) activity (half-wave potential of 0.901 V vs. RHE). Theoretical calculations verify that selective carbon cleavage near Co centers can efficiently lower the overall ORR theoretical overpotential in comparison with intact atomic configuration.

Negative Pressure Pyrolysis Induced Highly Accessible Single Sites Dispersed on 3D Graphene Frameworks for Enhanced Oxygen Reduction

AbstractHerein, we report a negative pressure pyrolysis to access dense single metal sites (Co, Fe, Ni etc.) with high accessibility dispersed on three‐dimensional (3D) graphene frameworks (GFs), during which the differential pressure between inside and outside of metal–organic frameworks (MOFs) promotes the cleavage of the derived carbon layers and gradual expansion of mesopores. In situ transmission electron microscopy and Brunauer–Emmett–Teller tests reveal that the formed 3D GFs possess an enhanced mesoporosity and external surface area, which greatly favor the mass transport and utilization of metal sites. This contributes to an excellent oxygen reduction reaction (ORR) activity (half‐wave potential of 0.901 V vs. RHE). Theoretical calculations verify that selective carbon cleavage near Co centers can efficiently lower the overall ORR theoretical overpotential in comparison with intact atomic configuration.

Solvation and Mobilization of Copper Active Sites in Zeolites by Ammonia: Consequences for the Catalytic Reduction of Nitrogen Oxides.

ConspectusCopper-exchanged chabazite (Cu-CHA) zeolites are catalysts used in diesel emissions control for the abatement of nitrogen oxides (NOx) via selective catalytic reduction (SCR) reactions with ammonia as the reductant. The discovery of these materials in the early 2010s enabled a step-change improvement in diesel emissions aftertreatment technology. Key advantages of Cu-CHA zeolites over prior materials include their effectiveness at the lower temperatures characteristic of diesel exhaust, their durability under high-temperature hydrothermal conditions, and their resistance to poisoning from residual hydrocarbons present in exhaust. Fundamental catalysis research has since uncovered mechanistic and kinetic features that underpin the ability of Cu-CHA to selectively reduce NOx under strongly oxidizing conditions and to achieve improved NOx conversion relative to other zeolite frameworks, particularly at low exhaust temperatures and with ammonia instead of other reductants.One critical mechanistic feature is the NH3 solvation of exchanged Cu ions at low temperatures (<523 K) to create cationic Cu-amine coordination complexes that are ionically tethered to anionic Al framework sites. This ionic tethering confers regulated mobility that facilitates interconversion between mononuclear and binuclear Cu complexes, which is necessary to propagate SCR through a Cu2+/Cu+ redox cycle during catalytic turnover. This dynamic catalytic mechanism, wherein single and dual metal sites interconvert to mediate different half-reactions of the redox cycle, combines features canonically associated with homogeneous and heterogeneous reaction mechanisms.In this Account, we describe how a unified experimental and theoretical interrogation of Cu-CHA catalysts in operando provided quantitative evidence of regulated Cu ion mobility and its role in the SCR mechanism. This approach relied on new synthetic methods to prepare model Cu-CHA zeolites with varied active-site structures and spatial densities in order to verify that the kinetic and mechanistic models describe the catalytic behavior of a family of materials of diverse composition, and on new computational approaches to capture the active-site structure and dynamics under conditions representative of catalysis. Ex situ interrogation revealed that the Cu structure depends on the conditions for the zeolite synthesis, which influence the framework Al substitution patterns, and that statistical and electronic structure models can enumerate Cu site populations for a known Al distribution. This recognition unifies seemingly disparate spectroscopic observations and inferences regarding Cu ion structure and responses to different external conditions. SCR rates depend strongly on the Cu spatial density and zeolite composition in kinetic regimes where Cu+ oxidation with O2 becomes rate-limiting, as occurs at lower temperatures and under fuel-rich conditions. Transient experiments, ab initio molecular dynamics simulations, and statistical models relate these sensitivities to the mobility constraints imposed by the CHA framework on NH3-solvated Cu ions, which regulate the pore volume accessible to these ions and their ability to pair and complete the catalytic cycle. This highlights the key characteristics of the CHA framework that enable superior performance under low-temperature SCR reaction conditions.This work illustrates the power of precise control over a catalytic material, simultaneous kinetic and spectroscopic interrogation over a wide range of reaction conditions, and computational strategies tailored to capture those reaction conditions to reveal in microscopic detail the mechanistic features of a complex and widely practiced catalysis. In doing so, it highlights the key role of ion mobility in catalysis and thus potentially a more general phenomenon of reactant solvation and active site mobilization in reactions catalyzed by exchanged metal ions in zeolites.

Boosting CO2 Conversion with Terminal Alkynes by Molecular Architecture of Graphene Oxide-Supported Ag Nanoparticles

Summary Carboxylation of terminal alkynes with CO2 via direct C–H bond activation is a highly appealing way to capture and convert CO2 but faces great challenges and difficulty. Here, we report an efficient catalyst that is prepared simply through introduction of p-tert-butylaniline into graphite oxide powders followed by localized growth of Ag nanoparticles (NPs). The bulky nature of p-tert-butylaniline facilitates the powder exfoliation, giving rise to mass production of uniform modified graphene oxide (tert-GO) nanosheets of 4 nm in thickness. Notably, Ag/tert-GO shows excellent catalytic activity for converting alkynes regardless of containing electron-donating or electron-withdrawing groups under mild reaction conditions. The synergy of the amide linkages on tert-GO nanosheets and the supported small-sized Ag NPs is recognized as the vital role in promoting adsorption of CO2 and subsequent conversion.

Structural Regulation and Support Coupling Effect of Single‐Atom Catalysts for Heterogeneous Catalysis

AbstractSingle atom catalysts (SACs) that integrate the merits of homogeneous and heterogeneous catalysts have been attracting considerable attention in recent years. The individual metal atoms of SACs can be stabilized on supports through various unsaturated chemical sites or space confinement for achieving the maximized atom utilization efficiency. Aside from the development of strategies for preparing high loading and high purity SACs, another key challenge in this field is precisely manipulating the geometric and electronic structure of catalytically active single metal sites, thus rendering the catalysts exceptionally reactive, selective, and stabile compared to their bulk counterparts. This review summarizes recent advancements in SACs for heterogeneous catalysis from the perspective of local structural regulation and the synergistic coupling effect between metal species and supports. Special emphasis is placed on the elucidation of the catalytic structure‐performance relationship in terms of coordination environment, valence state and metal‐support interactions by advanced characterization and theoretical studies. Select in situ or operando characterization techniques for tracking the SACs’ structure evolution under realistic conditions are highlighted. Finally, the challenges and opportunities are discussed to offer insight into the rational design of more intriguing SACs with high activity and distinct chemoselectivity.

P-block single-metal-site tin/nitrogen-doped carbon fuel cell cathode catalyst for oxygen reduction reaction.

This contribution reports the discovery and analysis of a p-block Sn-based catalyst for the electroreduction of molecular oxygen in acidic conditions at fuel cell cathodes; the catalyst is free of platinum-group metals and contains single-metal-atom actives sites coordinated by nitrogen. The prepared SnNC catalysts meet and exceed state-of-the-art FeNC catalysts in terms of intrinsic catalytic turn-over frequency and hydrogen-air fuel cell power density. The SnNC-NH3 catalysts displayed a 40-50% higher current density than FeNC-NH3 at cell voltages below 0.7 V. Additional benefits include a highly favourable selectivity for the four-electron reduction pathway and a Fenton-inactive character of Sn. A range of analytical techniques combined with density functional theory calculations indicate that stannic Sn(IV)Nx single-metal sites with moderate oxygen chemisorption properties and low pyridinic N coordination numbers act as catalytically active moieties. The superior proton-exchange membrane fuel cell performance of SnNC cathode catalysts under realistic, hydrogen-air fuel cell conditions, particularly after NH3 activation treatment, makes them a promising alternative to today's state-of-the-art Fe-based catalysts.

Cross‐Linked Polyphosphazene Hollow Nanosphere‐Derived N/P‐Doped Porous Carbon with Single Nonprecious Metal Atoms for the Oxygen Reduction Reaction

Heteroatom-doped polymers or carbon nanospheres have attracted broad research interest. However, rational synthesis of these nanospheres with controllable properties is still a great challenge. Herein, we develop a template-free approach to construct cross-linked polyphosphazene nanospheres with tunable hollow structures. As comonomers, hexachlorocyclotriphosphazene provides N and P atoms, tannic acid can coordinate with metal ions, and the replaceable third comonomer can endow the materials with various properties. After carbonization, N/P-doped mesoporous carbon nanospheres were obtained with small particle size (≈50 nm) and high surface area (411.60 m2 g-1 ). Structural characterization confirmed uniform dispersion of the single atom transition metal sites (i.e., Co-N2 P2 ) with N and P dual coordination. Electrochemical measurements and theoretical simulations revealed the oxygen reduction reaction performance. This work provides a solution for fabricating diverse heteroatom-containing polymer nanospheres and their derived single metal atom doped carbon catalysts.

Cross‐Linked Polyphosphazene Hollow Nanosphere‐Derived N/P‐Doped Porous Carbon with Single Nonprecious Metal Atoms for the Oxygen Reduction Reaction

AbstractHeteroatom‐doped polymers or carbon nanospheres have attracted broad research interest. However, rational synthesis of these nanospheres with controllable properties is still a great challenge. Herein, we develop a template‐free approach to construct cross‐linked polyphosphazene nanospheres with tunable hollow structures. As comonomers, hexachlorocyclotriphosphazene provides N and P atoms, tannic acid can coordinate with metal ions, and the replaceable third comonomer can endow the materials with various properties. After carbonization, N/P‐doped mesoporous carbon nanospheres were obtained with small particle size (≈50 nm) and high surface area (411.60 m2 g−1). Structural characterization confirmed uniform dispersion of the single atom transition metal sites (i.e., Co‐N2P2) with N and P dual coordination. Electrochemical measurements and theoretical simulations revealed the oxygen reduction reaction performance. This work provides a solution for fabricating diverse heteroatom‐containing polymer nanospheres and their derived single metal atom doped carbon catalysts.

Cation-Exchange Induced Precise Regulation of Single Copper Site Triggers Room-Temperature Oxidation of Benzene.

The controllable synthesis of stable single-metal site catalysts with an expected coordination environment for high catalytic activity and selectivity is still challenging. Here, we propose a cation-exchange strategy for precise production of an edge-rich sulfur (S) and nitrogen (N) dual-decorated single-metal (M) site catalysts (M = Cu, Pt, Pd, etc.) library. Our strategy relies on the anionic frameworks of sulfides and N-rich polymer shell to generate abundant S and N defects during high-temperature annealing, further facilitating the stabilization of exchanged metal species with atomic dispersion and excellent accessibility. This process was traced by in situ transmission electron microscopy, during which no metal aggregates were observed. Both experiments and theoretical results reveal the precisely obtained S, N dual-decorated Cu sites exhibit a high activity and low reaction energy barrier in catalytic hydroxylation of benzene at room temperature. These findings provide a route to controllably produce stable single-metal site catalysts and an engineering approach for regulating the central metal to improve catalytic performance.

Evolution of Zn(II) single atom catalyst sites during the pyrolysis-induced transformation of ZIF-8 to N-doped carbons

The pyrolysis of zeolitic imidazolate frameworks (ZIFs) is becoming a popular approach for the synthesis of catalysts comprising porphyrin-like metal single atom catalysts (SACs) on N-doped carbons (M-N-C). Understanding the structural evolution of M-N-C as a function of ZIF pyrolysis temperature is important for realizing high performance catalysts. Herein, we report a detailed investigation of the evolution of Zn single atom catalyst sites during the pyrolysis of ZIF-8 at temperatures ranging from 500 to 900 °C. Results from Zn L-edge and Zn K-edge X-ray absorption spectroscopy studies reveal that tetrahedral ZnN4 centers in ZIF-8 transform to porphyrin-like ZnN4 centers supported on N-doped carbon at temperatures as low as 600 °C. As the pyrolysis temperature increased in the range 600–900 °C, the Zn atoms moved closer to the N4 coordination plane. This subtle geometry change in the ZnN4 sites alters the electron density on the Zn atoms (formally Zn2+), strongly impacting the catalytic performance for the peroxidase-like decomposition of H2O2. The catalyst obtained at 800 °C (Zn-N-C-800) offered the best performance for H2O2 decomposition. This work provides valuable new insights about the evolution of porphyrin-like single metal sites on N-doped carbons from ZIF precursors and the factors influencing SAC activity.

Highly Productive Electrosynthesis of Ammonia by Admolecule-Targeting Single Ag Sites.

The ambient electrocatalytic N2 reduction reaction (NRR) is a promising alternative to the Haber-Bosch process for producing NH3. However, a guideless search for single-atom-based and other electrocatalysts cannot promote the NH3 yield rates by NRR efficiently. Herein, our first-principles calculations reveal that the successive emergence of vertical end-on *N2 and oblique end-on *NNH admolecules on single metal sites is key to high-performance NRR. By targeting the admolecules, single Ag sites with the Ag-N4 coordination are found and synthesized massively. They exhibit a record-high NH3 yield rate (270.9 μg h-1 mgcat.-1 or 69.4 mg h-1 mgAg-1) and a desirable Faradaic efficiency (21.9%) in HCl aqueous solution under ambient conditions. The generation rate of NH3 is stable during 20 consecutive reaction cycles, and the reduction current density is almost constant for 60 h. This work provides an effective targeting-design principle to purposefully synthesize active and durable single-atom-based NRR electrocatalysts.

Metal-Organic Framework-Based Catalysts with Single Metal Sites.

Metal-organic frameworks (MOFs) are a class of distinctive porous crystalline materials constructed by metal ions/clusters and organic linkers. Owing to their structural diversity, functional adjustability, and high surface area, different types of MOF-based single metal sites are well exploited, including coordinately unsaturated metal sites from metal nodes and metallolinkers, as well as active metal species immobilized to MOFs. Furthermore, controllable thermal transformation of MOFs can upgrade them to nanomaterials functionalized with active single-atom catalysts (SACs). These unique features of MOFs and their derivatives enable them to serve as a highly versatile platform for catalysis, which has actually been becoming a rapidly developing interdisciplinary research area. In this review, we overview the recent developments of catalysis at single metal sites in MOF-based materials with emphasis on their structures and applications for thermocatalysis, electrocatalysis, and photocatalysis. We also compare the results and summarize the major insights gained from the works in this review, providing the challenges and prospects in this emerging field.

(Keynote) Noble-Metal-Free Nanostructured and Graphene Supported Electrocatalysts for Water Splitting

Clean hydrogen production through water splitting is a direct and promising sustainable energy pathway to access and store non-fossil chemical fuels. Synthetic design strategies to access low cost, robust and high performance noble metal-free electrocatalysts are vital for forthcoming water splitting applications. To accomplish this goal, the nanoscale design of multifunctional catalysts based on cost-effective graphene supports, hollow nano-architectures and well-coordinated hybrid organic-inorganic structures has been attracting increasing research interest because of the flexible tuning options of their electronic states, chemical composition and local coordination environments.Over the last years, we have been implementing systematic investigations based on synthetic design, spectroscopy approaches and computational modeling toward the understanding of the mechanism of action in a series of novel, robust and efficient bi-functional electrocatalysts.Recently, we explored synergistic effects of NiFe alloys encapsulated into N-doped carbon nanotubes (N-CNTs) supported on reduced graphene (rGO) nanoshets for overall water splitting.[1] This so-called NiFe-N-CNT-rGO electrocatalyst was synthesized through a direct and flexible strategy using g-C3N4 as precursor, where thermally reduced NiFe nanoparticles act as surface nucleation sites for C species to assist N-CNT growth through an unconventional reduction-nucleation-growth mechanism. The catalyst has a low overpotential of 270 mV for oxygen evolution reaction (OER), being superior in performance to a wide range of reported noble-metal-free catalysts. As revealed from density functional theory (DFT) calculations, N-doping and charge transfer at the CNT walls tune the free energy in the electronic structure toward adsorption of intermediates, which greatly enhanced catalytic performance. This synthetic strategy not only leads to excellent performance and opens up new avenues for other carbon-supported alloy catalysts, but its scalability and easy applicability also render it quite promising for large-scale water splitting applications.In parallel, we explored molecular strategies to conjugate single active sites of metal-phthalocyanine molecules MPc (M=Ni, Co, Fe) on GO.[2] We aim for a thorough understanding of the role of the local coordination environment around the single metal site in the synergistic mechanisms and the catalytic performance. With an advanced combination of ADF (annular dark field)-STEM, operando X-ray absorption spectroscopy and DFT calculations, we observed changes in the electronic and local structure environment of MPc-GO under operando electrochemical OER conditions. Single active metal Ni, Co, Fe sites attain high valence states due to chemisorbed OH− species upon catalytic activation, while the local orders suffer from structural distortion. These changes in the electronic and structural properties lead to the formation of HO-M-N4 moieties with high OER reactivity under operando conditions. These results provides new insight into the fundamental understanding of structure-performance relationships for single active site catalysts.Likewise, we studied hollow transition metal sulfide nanoboxes synthesized through anion exchange processes[3] between S2- and CN- species that lead to formation of Prussian blue (PB), M-S@PB (M=Co, Fe, Ni) heterostructures. We found that the high performance of those nanostructures arises from in situ formation of active Co-Fe oxide/hydroxide species during OER, attaining a superior performance compared to noble-metal-catalysts such as RuO2, with low overpotential of 286 mV and high durability over longer operational periods. The flexible tuning options of the electronic, chemical and local-atomic coordination of those nanostructures render them promising hybrid catalysts for dual OER and HER over an extended pH range.We have further explored new soft templating strategies for the first 1D cobalt coordination polymer electrocatalyst with bio-inspired features, and we applied state-of-the-art analytical techniques and computational modeling to monitor its formation in situ and to unravel its structure.[4] The highly durable 1D-cobalt coordination polymer catalyst implements strategies to transfer key motifs of inorganic materials into a hydrogen bonded ligand environment, namely the embedment of the essential {H2O-Co2(OH)2-OH2} edge-site motif of cobalt oxide catalysts into a flexible and robust organic matrix. While this unconventional catalyst shows exceptional performance in commercial alkaline electrolyzers and organic transformations, its flexible structure offers new pathways toward the rational design of mixed molecular-solid disordered catalysts.[1] W. Wan, S. Wei, J. Li, C. A. Triana, Y. Zhou, G. R. Patzke, J. Mater. Chem. A 2019 (7) 15145.[2] W. Wan, C. A. Triana, J. Lan, J. Li, C. S. Allen, Y. Zhao, M. Iannuzzi, G. R. Patzke, in preparation.[3] Y. Zhao, C. K. Mavrokefalos, P. Zhang, R. Erni, J. Li, C. A. Triana, G. R. Patzke, submitted.[4] C.A. Triana, R. More, A. J. Bloomfield, P. V. Petrovic, S. G. Ferroon, G. Stanley, S. D. Zaric, T. Fox, E. N. Brothers, S. W. Sheehan, P. T. Anastas, G. R. Patzke, Matter 2019 (1) 1354.

(Invited) Carbon-Based Single Ni Site Catalysts for Nitrogen Reduction Toward Electrochemical Ammonia Synthesis

Ammonia electrosynthesis using nitrogen and water has been attracting significant attention and can be easily used for distributed fertilizer production or fuel generation. However, electrochemically nitrogen reduction reaction (NRR) under ambient conditions is very challenging and largely dependent on active and selective catalysts. Herein, we report a new class of atomically dispersed Ni site catalyst, which exhibited the highest ammonia yield of 112 µg cm-2h-1 and a FE of 20 % in neutral electrolyte. The coordination of Ni sites with nitrogen was further verified by advanced X-ray absorption spectroscopy and electron microscopy, suggesting a coordination number close to 3. Density functional theory calculations provide insightful understanding on the possible structure of active sites and the relevant reaction pathway of the NRR on the single Ni site catalysts. Although we are not able to do the very expensive 15N2 isotope tests, extensive controls strongly suggest the atomically dispersed Ni-Nx-C coordination provides more intrinsically active sites than those in N-doped carbon for ammonia production throng the NRR, instead of possible environmental contamination. This work further supports that single metal sites catalyst with appropriate nitrogen coordination is very promising for the NRR and indeed improve the scaling relationship of transition metals.