Recent Advanced Materials for Electrochemical and Photoelectrochemical Synthesis of Ammonia from Dinitrogen: One Step Closer to a Sustainable Energy Future

Ammonia (NH₃), an important raw material for chemical industry and agriculture, is also considered to be an intriguing energy storage and transportation media for chemical conversion schemes. The world's primary NH₃ supply is based on the natural nitrogen fixation by diazotrophs through an enzymatic nitrogenase process and the industrial nitrogen fixation through a traditional Haber–Bosch process. The natural synthesis of NH₃ can hardly meet the rapidly growing global demand. Meanwhile, the industrial NH₃ production is still dominated by the high‐temperature and high‐pressure reaction between nitrogen and hydrogen (N₂ + 3H₂ → 2NH₃), requiring intensive energy input and generating massive CO₂. Therefore, seeking a breakthrough in the development of catalysts toward efficient ammonia synthesis has become the frontier of energy and chemical conversion schemes. This review summarizes and discusses the recent progress on developing new strategies to optimize the efficiency of NH₃ production coupled with renewable energy sources, with a specific focus on electrocatalytic and photoelectrocatalytic conversion of N₂ to NH₃. The most recent advances in the development of catalytic materials, the design of the reaction systems, and the computational insights for electrochemical and photoelectrochemical ammonia synthesis are covered.     

Dramatically Enhanced Ambient Ammonia Electrosynthesis Performance by In‐Operando Created Li–S Interactions on MoS2 Electrocatalyst

The Haber‐Bosch process can be replaced by the ambient electrocatalytic N₂ reduction reaction (NRR) to produce NH₃ if suitable electrocatalysts can be developed. However, to develop high performance N₂ fixation electrocatalysts, a key issue to be resolved is to achieve efficient hydrogenation of N₂ without interference by the thermodynamically favored hydrogen evolution reaction (HER). Herein, in‐operando created strong Li–S interactions are reported to empower the S‐rich MoS₂ nanosheets with superior NRR catalytic activity and HER suppression ability. The Li⁺ interactions with S‐edge sites of MoS₂ can effectively suppress hydrogen evolution reaction by reducing H* adsorption free energy from 0.03 to 0.47 eV, facilitate N₂ adsorption by increasing N₂ adsorption free energy from –0.32 to –0.70 eV and enhance electrocatalytic N₂ reduction activity by decreasing the activation energy barrier of the reaction control step (*N₂ → *N₂H) from 0.84 to 0.42 eV. A NH₃ yield rate of 43.4 μg h^?1 mg^?1 MoS₂ with a faradaic efficiency (FE) of 9.81% can be achieved in presence of strong Li–S interactions, more than 8 and 18 times by the same electrocatalyst in the absence of Li–S interactions. This report opens a new way to design and develop catalysts and catalysis systems.     

In Situ Fragmented Bismuth Nanoparticles for Electrocatalytic Nitrogen Reduction

The electrochemical nitrogen reduction reaction (NRR) is a promising alternative to the energy‐intensive Haber–Bosch process for ammonia synthesis. Among the possible electrocatalysts, bismuth‐based materials have shown unique NRR properties due to their electronic structures and poor hydrogen evolution activity. However, identification of the active sites and reaction mechanism is still difficult due to structural and chemical changes under reaction potentials. Herein, in situ Raman spectroscopy, complemented by electron microscopy, is employed to investigate the structural and chemical transformation of the Bi species during the NRR. Nanorod‐like bismuth‐based metal–organic frameworks are reduced in situ and fragment into densely contacted Bi⁰ nanoparticles under the applied potentials. The fragmented Bi⁰ nanoparticles exhibit excellent NRR performance in both neutral and acidic electrolytes, with an ammonia yield of 3.25 ± 0 .08 µg cm^?2 h^?1 at ?0.7 V versus reversible hydrogen electrode and a Faradaic efficiency of 12.11 ± 0.84% at ?0.6 V in 0.10 m Na₂SO₄. Online differential electrochemical mass spectrometry detects the production of NH₃ and N₂H₂ during NRR, suggesting a possible pathway through two‐step reduction and decomposition. This work highlights the importance of monitoring and optimizing the electronic and geometric structures of the electrocatalysts under NRR conditions.     

Anchoring PdCu Amorphous Nanocluster on Graphene for Electrochemical Reduction of N2 to NH3 under Ambient Conditions in Aqueous Solution

As an alternative approach for N₂ fixation under milder conditions, electrocatalytic nitrogen reduction reaction (NRR) represents a very attractive strategy for sustainable development and N₂ cycle to store and utilize energy from renewable sources. However, the research on NRR electrocatalysts still mainly focuses on noble metals, while, high costs and limited resources greatly restrict their large‐scale applications. Herein, as a proof‐of‐concept experiment, taking PdCu amorphous nanocluster anchored on reduced graphene oxide (rGO) as NRR catalysts, the optimum Pd_0.2Cu_0.8/rGO composite presents a synergistic effect and shows superior electrocatalytic performance toward NRR under ambient conditions (yield: 2.80 µg h^?1 mg_cat.^?1 at ?0.2 V vs reversible hydrogen electrode), which is much higher than that of monometallic, especially noble metal, counterparts. The superior catalytic performance of alloy catalysts with low noble metal loading would strongly spur interest toward more researches on NRR catalysts in the future.     

INTERACTION OF NITROGEN FIXATION AND PHOSPHORUS LIMITATION IN APHANIZOMENON FLOS-AQUAE (CYANOPHYCEAE)1

The effect of simultaneous nitrogen fixation and phosphorus limitation on the physiological adaptation and growth performance of Aphanizomenon flos-aquae (L.) Ralfs PCC 7905 was studied in continuous culture. In the absence of ammonia, N₂ fixation occurred and the maximum growth rate (as determined in diluted batch cultures) was lower. However, no distinction could be made between the steady-state N uptake rates (based on cellular N contents) of N₂-fixing cells and cells grown with ammonia. At the higher dilution rates, the residual P concentration increased with increasing dilution rate, more so under N₂-fixing conditions, compared to the cultures grown in the presence of ammonia. More generally, the yield of biomass per consumed P, as the biomass concentration itself, decreased with increasing dilution rate, and both were lower under N₂-fixing conditions. The restricted biomass production under N₂-fixing conditions suggests that reduction of N loading may benefit lake restoration projects. The influence of N₂-fixation on the severity of P limitation is discussed in terms of metabolic control analysis. From the increase of the residual P concentration on switching from ammonium to N₂-fixing conditions, it is deduced that under N₂-fixing and P-limited conditions, control of growth is shared by N and P metabolism.     

An In situ Proton Filter Covalent Organic Framework Catalyst for Highly Efficient Aqueous Electrochemical Ammonia Production

The electrocatalytic nitrogen reduction reaction (NRR) driven by renewable electricity provides a green synthesis route for ammonia (NH₃) production under ambient conditions but suffers from a low conversion yield and poor Faradaic efficiency (F.E.) because of strong competition from hydrogen evolution reaction (HER) and the poor solubility of N₂ in aqueous systems. Herein, an in situ proton filter covalent organic framework catalyst ( Ru-Tta-Dfp ) is reported with inherent Ruthenium (Ru) sites where the framework controls reactant diffusion by suppressing proton supply and enhancing N₂ flux, causing highly selective and efficient catalysis. The smart catalyst design results in a remarkable ammonia production yield rate of 2.03 mg h⁻¹ mg_cat⁻¹ with an excellent F.E. of ≈52.9%. The findings are further endorsed with the help of molecular dynamics simulations and control COF systems without in situ proton filter feasibility. The results point to a paradigm shift in engineering high-performance NRR electrocatalysts for more feasible green NH₃ production.     

A Review of Electrocatalytic Reduction of Dinitrogen to Ammonia under Ambient Conditions

The production of ammonia (NH₃) from molecular dinitrogen (N₂) under mild conditions is one of the most attractive topics in the field of chemistry. Electrochemical reduction of N₂ is promising for achieving clean and sustainable NH₃ production with lower energy consumption using renewable energy sources. To date, emerging electrocatalysts for the electrochemical reduction of N₂ to NH₃ at room temperature and atmospheric pressure remain largely underexplored. The major challenge is to achieve both high catalytic activity and high selectivity. Here, the recent progress on the electrochemical nitrogen reduction reaction (NRR) at ambient temperature and pressure from both theoretical and experimental aspects is summarized, aiming at extracting instructive perceptions for future NRR research activities. The prevailing theories and mechanisms for NRR as well as computational screening of promising materials are presented. State‐of‐the‐art heterogeneous electrocatalysts as well as rational design of the whole electrochemical systems for NRR are involved. Importantly, promising strategies to enhance the activity, selectivity, efficiency, and stability of electrocatalysts toward NRR are proposed. Moreover, ammonia determination methods are compared and problems relating to possible ammonia contamination of the system are mentioned so as to shed fresh light on possible standard protocols for NRR measurements.     

Effects of modified nutrient concentrations and ratios on the structure and function of the native phytoplankton community in the Neuse River Estuary, North Carolina, USA

A variety of analyses were used to assess the structure (community composition) and function (assimilation number, nitrogen fixation) of phytoplankton in the Neuse River Estuary (NRE), NC under ambient and modified nutrient concentrations. Dilution bioassays were employed to reduce the concentration of nitrogen (N) or both N and phosphorus (P) and thus compare varied DIN:DIP ratios. Experimental manipulations created conditions that may result from mandated N load reductions to the estuary. We hypothesized that unilateral reduction of N loading to the NRE would increase the activity, abundance and diversity of N₂ fixing cyanobacteria. Changes in phytoplankton primary productivity, N₂ fixation (nitrogenase activity), genetic potential for N₂ fixation (presence of nifH), phytoplankton taxonomic composition (diagnostic photopigment concentration) and abundances of N₂ fixing cyanobacteria (microscopy) were determined. Decreasing ambient DIN:DIP ratios in NRE samples resulted in increased rates of N₂ fixation when seed populations were present and environmental conditions were amenable. Decreasing the DIN:DIP ratio did not lead to an increase in the abundance or diversity of N₂ fixing cyanobacteria. Because N₂ fixing cyanobacteria were only actively fixing nitrogen during periods of low riverine N discharge (summer and early autumn), lowering nutrient ratios may not have a major impact on the NRE. However, the maximum potential amount of N from N₂ fixation was calculated using rates from this study and was found to be approximately 3% of total riverine loading of N to the NRE. Because N₂ fixation occurs farther downstream and later in the year than riverine N loading to the NRE, there is potential for N₂ fixation to modify N dynamics. Analyses of the phytoplankton community as a whole in these relatively short term experiments indicated that reduced DIN:DIP may not have a major impact on their structure and function.     

Effect of fermentation conditions on N2 fixation by Methylococcus capsulatus

Nitrogen fixation has been investigated during chemostat fermentations with a culture of Methylococcus capsulatus with natural gas. It is demonstrated that nitrogen fixation occurs under conditions when either nitrate or ammonia as nitrogen source is insufficient for the growth on fixed supply of methane and oxygen. The fixation occurs contrary to expectations within a wide range of dilution rates and with variation of concentration of liquid source of nitrogen. An O₂ optimum is determined for the nitrogenase system of the culture in an assay. During fermentation a complete abolishment of nitrogenase reaction is attained at 15% air saturation (dissolved oxygen). Conditions for N₂ fixation is unaltered with change of pH from 6.8 to 5.7.     

Hydrogen inhibition of nitrogen reduction by nitrogenase in isolated soybean nodule bacteroids

Dihydrogen, a by-product of biological nitrogen fixation, is a competitive inhibitor of N₂ reduction by nitrogenase. To evaluate the significance of H₂ inhibition in vivo, we have measured the apparent inhibition constant for H₂ inhibition of N₂ reduction in Bradyrhizobium japonicum bacteroids isolated from soybean nodules. The rate of N₂ reduction was measured as ammonia production by bacteroids incubated in a buffer containing 200 micromolar leghemoglobin and 10 millimolar succinate under 0.02 atmosphere O₂ and various concentrations of N₂ and H₂. The apparent inhibition constant for H₂ under these conditions was determined to be approximately 0.03 atmosphere. This relatively low value strengthens the proposal that H₂ inhibition of N₂ reduction may be a significant factor in lowering the efficiency of nitrogen fixation in legume nodules.     

Spontaneous Atomic Ruthenium Doping in Mo2CTX MXene Defects Enhances Electrocatalytic Activity for the Nitrogen Reduction Reaction

The electrochemical nitrogen reduction reaction (NRR) process usually suffers extremely low Faradaic efficiency and ammonia yields due to sluggish N?N dissociation. Herein, single‐atomic ruthenium modified Mo₂CT_X MXene nanosheets as an efficient electrocatalyst for nitrogen fixation at ambient conditions are reported. The catalyst achieves a Faradaic efficiency of 25.77% and ammonia yield rate of 40.57 µg h^?1 mg^?1 at ‐0.3 V versus the reversible hydrogen electrode in 0.5 m K₂SO₄ solution. Operando X‐ray absorption spectroscopy studies and density functional theory calculations reveal that single‐atomic Ru anchored on MXene nanosheets act as important electron back‐donation centers for N₂ activation, which can not only promote nitrogen adsorption and activation behavior of the catalyst, but also lower the thermodynamic energy barrier of the first hydrogenation step. This work opens up a promising avenue to manipulate catalytic performance of electrocatalysts utilizing an atomic‐level engineering strategy.     

Nitrogen Fixation by the Photosynthetic Sulfur Bacterium Chlorobium phaeobacteroides from Lake Kinneret

N₂ fixation by Chlorobium phaeobacteroides from Lake Kinneret was dependent on ammonia concentration and light intensity. In the thermocline of Lake Kinneret, N₂ fixation and photosynthesis were low. It was concluded that the bacteria do not contribute significantly to the organic nitrogen load of the lake.     

Soybean nodulation and N2 fixation response to drought under carbon dioxide enrichment

The combined effects of carbon dioxide (CO₂) enrichment and water deficits on nodulation and N₂ fixation were analysed in soybean [Glycine max (L.) Merr.]. Two short-term experiments were conducted in greenhouses with plants subjected to soil drying, while exposed to CO₂ atmospheres of either 360 or 700 μmol CO₂ mol^–1. Under drought-stressed conditions, elevated [CO₂] resulted in a delay in the decrease in N₂ fixation rates associated with drying of the soil used in these experiments. The elevated [CO₂] also allowed the plants under drought to sustain significant increases in nodule number and mass relative to those under ambient [CO₂]. The total non-structural carbohydrate (TNC) concentration was lower in the shoots of the plants exposed to drought; however, plants under elevated CO₂ had much higher TNC levels than those under ambient CO₂. For both [CO₂] treatments, drought stress induced a substantial accumulation of TNC in the nodules that paralleled N₂ fixation decline, which indicates that nodule activity under drought may not be carbon limited. Under drought stress, ureide concentration increased in all plant tissues. However, exposure to elevated [CO₂] resulted in substantially less drought-induced ureide accumulation in leaf and petiole tissues. A strong negative correlation was found between ureide accumulation and TNC levels in the leaves. This relationship, together with the large effect of elevated [CO₂] on the decrease of ureide accumulation in the leaves, indicated the importance of ureide breakdown in the response of N₂ fixation to drought and of feedback inhibition by ureides on nodule activity. It is concluded that an important effect of CO₂ enrichment on soybean under drought conditions is an enhancement of photoassimilation, an increased partitioning of carbon to nodules and a decrease of leaf ureide levels, which is associated with sustained nodule growth and N₂ rates under soil water deficits. We suggest that future [CO₂] increases are likely to benefit soybean production by increasing the drought tolerance of N₂ fixation.     

Comparative adaptations of Aphanizomenon and Anabaena for nitrogen fixation under weak irradiance

1. In situ measurements of nitrogen fixation rates for Aphanizomenon in fertile Colorado lakes with low inorganic nitrogen concentrations demonstrated high efficiency of nitrogen fixation at low irradiance. 2. For study populations, rates of N₂ fixation in darkness and with alternating exposure to light and darkness were a higher percentage of light‐saturated rates for Aphanizomenon than for Anabaena, suggesting storage of reduced metabolites at high irradiance that are used subsequently by Aphanizomenon when cells are forced by mixing into zones of low irradiance. Also, saturation of N₂ fixation occurred over a lower range of irradiance for Aphanizomenon than for Anabaena. 3. High efficiency of N₂ fixation in Aphanizomenon at low or fluctuating irradiance is complementary to its previously demonstrated high efficiency of photosynthesis at low irradiance. Nitrogen fixation rate was also strongly related to DIN concentration; fixation was highest at low DIN (maximum < 5 μg L^?1) but was also most vulnerable to photoinhibition under such conditions. 4. The fixation capabilities of Aphanizomenon under weak or varying irradiance could explain its commonly observed domination over Anabaena when transparency is low and available nitrogen is scarce.     

Nutrient Biogeochemistry During the Early Stages of Delta Development in the Mississippi River Deltaic Plain

Nutrient biogeochemistry associated with the early stages of soil development in deltaic floodplains has not been well defined. Such a model should follow classic patterns of soil nutrient pools described for alluvial ecosystems that are dominated by mineral matter high in phosphorus and low in carbon and nitrogen. A contrast with classic models of soil development is the anthropogenically enriched high nitrate conditions due to agricultural fertilization in upstream watersheds. Here we determine if short-term patterns of soil chemistry and dissolved inorganic nutrient fluxes along the emerging Wax Lake delta (WLD) chronosequence are consistent with conceptual models of long-term nutrient availability described for other ecosystems. We add a low nitrate treatment more typical of historic delta development to evaluate the role of nitrate enrichment in determining the net dinitrogen (N₂) flux. Throughout the 35-year chronosequence, soil nitrogen and organic matter content significantly increased by an order of magnitude, whereas phosphorus exhibited a less pronounced increase. Under ambient nitrate concentrations (>60 μM), mean net N₂ fluxes (157.5 μmol N m^?2 h^?1) indicated greater rates of gross denitrification than gross nitrogen fixation; however, under low nitrate concentrations (<2 μM), soils switched from net denitrification to net nitrogen fixation (?74.5 μmol N m^?2 h^?1). As soils in the WLD aged, the subsequent increase in organic matter stimulated net N₂, oxygen, nitrate, and nitrite fluxes producing greater fluxes in more mature soils. In conclusion, soil nitrogen and carbon accumulation along an emerging delta chronosequence largely coincide with classic patterns of soil development described for alluvial floodplains, and substrate age together with ambient nitrogen availability can be used to predict net N₂ fluxes during early delta evolution.     

Metal limitation of cyanobacterial N2 fixation and implications for the Precambrian nitrogen cycle

Nitrogen fixation is a critical part of the global nitrogen cycle, replacing biologically available reduced nitrogen lost by denitrification. The redox‐sensitive trace metals Fe and Mo are key components of the primary nitrogenase enzyme used by cyanobacteria (and other prokaryotes) to fix atmospheric N₂ into bioessential compounds. Progressive oxygenation of the Earth's atmosphere has forced changes in the redox state of the oceans through geologic time, from anoxic Fe‐enriched waters in the Archean to partially sulfidic deep waters by the mid‐Proterozoic. This development of ocean redox chemistry during the Precambrian led to fluctuations in Fe and Mo availability that could have significantly impacted the ability of prokaryotes to fix nitrogen. It has been suggested that metal limitation of nitrogen fixation and nitrate assimilation, along with increased rates of denitrification, could have resulted in globally reduced rates of primary production and nitrogen‐starved oceans through much of the Proterozoic. To test the first part of this hypothesis, we grew N₂‐fixing cyanobacteria in cultures with metal concentrations reflecting an anoxic Archean ocean (high Fe, low Mo), a sulfidic Proterozoic ocean (low Fe, moderate Mo), and an oxic Phanerozoic ocean (low Fe, high Mo). We measured low rates of cellular N₂ fixation under [Fe] and [Mo] estimated for the Archean ocean. With decreased [Fe] and higher [Mo] representing sulfidic Proterozoic conditions, N₂ fixation, growth, and biomass C:N were similar to those observed with metal concentrations of the fully oxygenated oceans that likely developed in the Phanerozoic. Our results raise the possibility that an initial rise in atmospheric oxygen could actually have enhanced nitrogen fixation rates to near modern marine levels, providing that phosphate was available and rising O₂ levels did not markedly inhibit nitrogenase activity.     

Substrate and light dependent fixation of molecular nitrogen in Rhodospirillum rubrum

Summary Whole cells of Rhodospirillum rubrum were cultivated in a malate medium lacking bound nitrogen under N₂ and tested for their nitrogenase activity by measuring the disappearance of nitrogen manometrically.Several experimental conditions were relevant in maintaining consistently high activities. These included: a) light intensity, b) substrate concentration, c) concentration of the cell suspension, d) buffer molarity, pH, and e) temperature.Under our optimal experimental conditions about 6 moles of either l-malate, fumarate, succinate or 10 moles of pyruvate were consumed per 1 mole of molecular nitrogen.The amount of gas taken up by the cells agreed quantitatively with the increase of bound nitrogen found in the cells by microkjeldahl determinations.The fixation of molecular nitrogen is suppresed quickly and specifically by very small amounts of ammonia (<5 g ammonia N/ml). The duration of this inhibition depends on the amount of ammonia available to the cells.     

Nitrogen fixation as evidence for the reducing nature of the early biosphere

Probably the first nitrogen fixers were anaerobic, non-photosynthetic, bacteria, i.e. fermenters. During the evolution of N₂ fixation they still needed nitrogen on the oxidation level of ammonia. Because of the complexities in structure and function of nitrogenase this evolution must have required a long time. The photosynthetic and later the respiring bacteria inherited the capacity for N₂ fixation from the fermenters, but the process did not change a great deal when it was taken over.Because of the long need for NH₃, which is unstable in a redoxneutral atmosphere, a long-persisting reducing atmosphere was needed. The transition to a redoxneutral atmosphere, dominated by CO₂, H₂O and N₂, cannot have been rapid, and the NH₃ in it was recycled. Probably the atmosphere contained for a long time, as was suggested by Urey but is often denied now, a great deal of methane as a reductant. The recycling occurred with participation of intermediates like cyanide, through energy input as UV radiation or as electric discharges. A stationary state was set up.The hypothesis is recalled that coloured, photosynthetic, NH₃ bacteria, analogous to coloured sulphur bacteria, may have existed, or may still exist, in reducing conditions. A few remarks are made about the origin of nitrification in the later, oxidizing atmosphere.     

Divergent selection for dinitrogen fixation and yield in soybean

Summary Nitrogen fixation is generally considered to be a major parameter of productivity in soybean (Glycine max). The aim of the investigations reported here was to analyse the genetic behaviour of this trait in view of its possible use as an indirect criterion of selection for productivity. Divergent selection for nitrogen fixation rate was carried out on F₂ populations obtained from crosses between high-yielding cultivars that are well adapted to French climatic conditions. The genetic component of nitrogen fixation and yield was isolated through the analysis of (1) the nitrogen fixation potentials of the genotypes under controlled conditions and (2) the field yields under favourable conditions. Divergent selection resulted in two groups of genotypes whose nitrogen fixation abilities are significantly different. The F₆ filial progeny obtained by single seed descent from the two groups displayed significantly different abilities for nitrogen fixation and for field productivity. The gain achieved for the nitrogen fixation activity with respect to the mean value of the parents ranged from 20% to 33% for the positive selection, depending on the crosses. The occurrence of positive and significant correlations between the level of nitrogen fixation activity in F₂ plants and N₂ fixation or yield in the F₆ generation corroborates the relatively high heritability of this trait and suggests its possible use as an indirect selection criterion for yield.