Electrochemical Fabrication of Porous Au Film on Ni Foam for Nitrogen Reduction to Ammonia

Electrochemical reduction of N₂ to NH₃ provides an alternative strategy to replace the industrial Haber–Bosch process for facile and sustainable production of NH₃. The development of efficient electrocatalysts for the nitrogen reduction reaction (NRR) is highly desired. Herein, a micelle‐assisted electrodeposition method is presented for the direct fabrication of porous Au film on Ni foam (pAu/NF). Benefiting from its interconnected porous architectonics, the pAu/NF exhibits superior NRR performance with a high NH₃ yield rate of 9.42 µg h^?1 cm^?2 and a superior Faradaic efficiency of 13.36% at ?0.2 V versus reversible hydrogen electrode under the neutral electrolyte (0.1 m Na₂SO₄). The proposed micelle‐assisted electrodeposition strategy is highly valuable for future design of active NRR catalysts with desired compositions toward various electrocatalysis fields.     

Salt‐Templated Construction of Ultrathin Cobalt Doped Iron Thiophosphite Nanosheets toward Electrochemical Ammonia Synthesis

Exploiting efficient electrocatalysts for electrochemical nitrogen reduction (NRR) is highly desired and deeply meaningful for realizing sustainable ammonia (NH₃) production under ambient conditions. The Fe protein contains one [Fe₄S₄] cluster and P cluster, which play an important role for transfer electron during the nitrogen fixing of nitrogenases. Based on the understanding of nitrogenase, the rising‐star 2D iron thiophosphite (FePS₃) nanomaterials may be highly active electrocatalysts toward NRR due to the ideal elemental composition. In this work, 2D FePS₃ nanosheets are successfully synthesized by a facile salt‐templated method. The FePS₃ nanosheets show better electrocatalytic NH₃ yield and faradaic efficiency (FE) than Fe₂S₃, which demonstrates that the P element indeed improves the NRR activity of Fe‐S. Theoretically, Co incorporation not only effectively prompts the conductivity of FePS₃, but also enhances the catalytic activities of Fe‐edge sites. Experimentally, Co‐doped FePS₃ (Co‐FePS₃) nanosheets exhibit a remarkable electrocatalytic performance toward NRR, such as high NH₃ yield rate of 90.6 µg h^?1 mg_cat^?1, high FE of 3.38%, and an excellent long‐term stability. Being the first theoretical and experimental report regarding FePS₃‐based electrocatalyst toward NRR, this work represents an important beginning to the family of metal thiophosphite as advanced electrocatalysts toward NRR.     

Photoactive Earth‐Abundant Iron Pyrite Catalysts for Electrocatalytic Nitrogen Reduction Reaction

The generation of ammonia, hydrogen production, and nitrogen purification are considered as energy intensive processes accompanied with large amounts of CO₂ emission. An electrochemical method assisted by photoenergy is widely utilized for the chemical energy conversion. In this work, earth‐abundant iron pyrite (FeS₂) nanocrystals grown on carbon fiber paper (FeS₂/CFP) are found to be an electrochemical and photoactive catalyst for nitrogen reduction reaction under ambient temperature and pressure. The electrochemical results reveal that FeS₂/CFP achieves a high Faradaic efficiency (FE) of ≈14.14% and NH₃ yield rate of ≈0.096 µg min^?1 at ?0.6 V versus RHE electrode in 0.25 m LiClO₄. During the electrochemical catalytic reaction, the crystal structure of FeS₂/CFP remains in the cubic pyrite phase, as analyzed by in situ X‐ray diffraction measurements. With near‐infrared laser irradiation (808 nm), the NH₃ yield rate of the FeS₂/CFP catalyst can be slightly improved to 0.1 µg min^?1 with high FE of 14.57%. Furthermore, density functional theory calculations demonstrate that the N₂ molecule has strong chemical adsorption energy on the iron atom of FeS₂. Overall, iron pyrite‐based materials have proven to be a potential electrocatalyst with photoactive behavior for ammonia production in practical applications.     

A Generalized Surface Chalcogenation Strategy for Boosting the Electrochemical N2 Fixation of Metal Nanocrystals

Electrocatalytic nitrogen reduction reaction (NRR) is a promising process relative to energy-intensive Haber–Bosch process. While conventional electrocatalysts underperform with sluggish paths, achieving dissociation of N₂ brings the key challenge for enhancing NRR. This study proposes an effective surface chalcogenation strategy to improve the NRR performance of pristine metal nanocrystals (NCs). Surprisingly, the NH₃ yield and Faraday efficiency (FE) (175.6 ± 23.6 mg h^–1 g^–1_Rh and 13.3 ± 0.4%) of Rh-Se NCs is significantly enhanced by 16 and 15 times, respectively. Detailed investigations show that the superior activity and high FE are attributed to the effect of surface chalcogenation, which not only can decrease the apparent activation energy, but also inhibit the occurrence of the hydrogen evolution reaction (HER) process. Theoretical calculations reveal that the strong interface strain effect within core@shell system induces a critical redox inversion, resulting in a rather low valence state of Rh and Se surface sites. Such strong correlation indicates an efficient electron-transfer minimizing NRR barrier. Significantly, the surface chalcogenation strategy is general, which can extend to create other NRR metal electrocatalysts with enhanced performance. This strategy open a new avenue for future NH₃ production for breakthrough in the bottleneck of NRR.     

Highly Selective N2 Electroreduction to NH3 Using a Boron-Vacancy-Rich Diatomic Nb?B Catalyst

The ambient electrochemical N₂ reduction reaction (NRR) is a future approach for the artificial NH₃ synthesis to overcome the problems of high-energy consumption and environmental pollution by Haber–Bosch technology. However, the challenge of N₂ activation on a catalyst surface and the competitive hydrogen evolution reaction make the current NRR unsatisfied. Herein, this work demonstrates that NbB₂ nanoflakes (NFs) exhibit excellent selectivity and durability in NRR, which produces NH₃ with a production rate of 30.5 µg h⁻¹ mg_cat⁻¹ and a super-high Faraday efficiency (FE) of 40.2%. The high-selective NH₃ production is attributed to the large amount of active B vacancies on the surface of NbB₂ NFs. Density functional theory calculations suggest that the multiple atomic adsorption of N₂ on both unsaturated Nb and B atoms results in a significantly stretched N₂ molecule. The weakened NN triple bonds are easier to be broken for a biased NH₃ production. The diatomic catalysis is a future approach for NRR as it shows a special N₂ adsorption mode that can be well engineered.     

Formation of B?N?C Coordination to Stabilize the Exposed Active Nitrogen Atoms in g‐C3N4 for Dramatically Enhanced Photocatalytic Ammonia Synthesis Performance

It is an important issue that exposed active nitrogen atoms (e.g., edge or amino N atoms) in graphitic carbon nitride (g‐C₃N₄) could participate in ammonia (NH₃) synthesis during the photocatalytic nitrogen reduction reaction (NRR). Herein, the experimental results in this work demonstrate that the exposed active N atoms in g‐C₃N₄ nanosheets can indeed be hydrogenated and contribute to NH₃ synthesis during the visible‐light photocatalytic NRR. However, these exposed N atoms can be firmly stabilized through forming B? N? C coordination by means of B‐doping in g‐C₃N₄ nanosheets (BCN) with a B‐doping content of 13.8 wt%. Moreover, the formed B? N? C coordination in g‐C₃N₄ not only effectively enhances the visible‐light harvesting and suppresses the recombination of photogenerated carriers in g‐C₃N₄, but also acts as the catalytic active site for N₂ adsorption, activation, and hydrogenation. Consequently, the as‐synthesized BCN exhibits high visible‐light‐driven photocatalytic NRR activity, affording an NH₃ yield rate of 313.9 µmol g^?1 h^?1, nearly 10 times of that for pristine g‐C₃N₄. This work would be helpful for designing and developing high‐efficiency metal‐free NRR catalysts for visible‐light‐driven photocatalytic NH₃ synthesis.     

B?N Pairs Enriched Defective Carbon Nanosheets for Ammonia Synthesis with High Efficiency

Electrochemical synthesis has garnered attention as a promising alternative to the traditional Haber–Bosch process to enable the generation of ammonia (NH₃) under ambient conditions. Current electrocatalysts for the nitrogen reduction reaction (NRR) to produce NH₃ are comprised of noble metals or transitional metals. Here, an efficient metal‐free catalyst (BCN) is demonstrated without precious component and can be easily fabricated by pyrolysis of organic precursor. Both theoretical calculations and experiments confirm that the doped B? N pairs are the active triggers and the edge carbon atoms near to B? N pairs are the active sites toward the NRR. This doping strategy can provide sufficient active sites while retarding the competing hydrogen evolution reaction (HER) process; thus, NRR with high NH₃ formation rate (7.75 µg h^?1 mg_cat. ^?1) and excellent Faradaic efficiency (13.79%) are achieved at ?0.3 V versus reversible hydrogen electrode (RHE), exceeding the performance of most of the metallic catalysts.     

Au Sub‐Nanoclusters on TiO2 toward Highly Efficient and Selective Electrocatalyst for N2 Conversion to NH3 at Ambient Conditions

As the N?N bond in N₂ is one of the strongest bonds in chemistry, the fixation of N₂ to ammonia is a kinetically complex and energetically challenging reaction and, up to now, its synthesis is still heavily relying on energy and capital intensive Haber–Bosch process (150–350 atm, 350–550 °C), wherein the input of H₂ and energy are largely derived from fossil fuels and thus result in large amount of CO₂ emission. In this paper, it is demonstrated that by using Au sub‐nanoclusters (≈0.5 nm ) embedded on TiO₂ (Au loading is 1.542 wt%), the electrocatalytic N₂ reduction reaction (NRR) is indeed possible at ambient condition. Unexpectedly, NRR with very high and stable production yield (NH₃: 21.4 µg h^?1 mg^?1_cat., Faradaic efficiency: 8.11%) and good selectivity is achieved at ?0.2 V versus RHE, which is much higher than that of the best results for N₂ fixation under ambient conditions, and even comparable to the yield and activation energy under high temperatures and/or pressures. As isolated precious metal active centers dispersed onto oxide supports provide a well‐defined system, the special structure of atomic Au cluster would promote other important reactions besides NRR for water splitting, fuel cells, and other electrochemical devices.     

Electrochemical Ammonia Synthesis via Nitrogen Reduction Reaction on a MoS2 Catalyst: Theoretical and Experimental Studies

The discovery of stable and noble‐metal‐free catalysts toward efficient electrochemical reduction of nitrogen (N₂) to ammonia (NH₃) is highly desired and significantly critical for the earth nitrogen cycle. Here, based on the theoretical predictions, MoS₂ is first utilized to catalyze the N₂ reduction reaction (NRR) under room temperature and atmospheric pressure. Electrochemical tests reveal that such catalyst achieves a high Faradaic efficiency (1.17%) and NH₃ yield (8.08 × 10^?11 mol s^?1 cm^?1) at ?0.5 V versus reversible hydrogen electrode in 0.1 m Na₂SO₄. Even in acidic conditions, where strong hydrogen evolution reaction occurs, MoS₂ is still active for the NRR. This work represents an important addition to the growing family of transition‐metal‐based catalysts with advanced performance in NRR.     

Constructing Ionic Gradient and Lithiophilic Interphase for High‐Rate Li‐Metal Anode

Li metal is the optimal choice as an anode due to its high theoretical capacity, but it suffers from severe dendrite growth, especially at high current rates. Here, an ionic gradient and lithiophilic inter‐phase film is developed, which promises to produce a durable and high‐rate Li‐metal anode. The film, containing an ionic‐conductive Li_0.33La_0.56TiO₃ nanofiber (NF) layer on the top and a thin lithiophilic Al₂O₃ NF layer on the bottom, is fabricated with a sol–gel electrospinning method followed by sintering. During cycling, the top layer forms a spatially homogenous ionic field distribution over the anode, while the bottom layer reduces the driving force of Li‐dendrite formation by decreasing the nucleation barrier, enabling dendrite‐free plating‐stripping behavior over 1000 h at a high current density of 5 mA cm^?2. Remarkably, full cells of Li//LiNi_0.8Co_0.15Al_0.05O₂ exhibit a high capacity of 133.3 mA h g^?1 at 5 C over 150 cycles, contributing a step forward for high‐rate Li‐metal anodes.     

Golden Bristlegrass‐Like Hierarchical Graphene Nanofibers Entangled with N‐Doped CNTs Containing CoSe2 Nanocrystals at Each Node as Anodes for High‐Rate Sodium‐Ion Batteries

Golden bristlegrass‐like unique nanostructures comprising reduced graphene oxide (rGO) matrixed nanofibers entangled with bamboo‐like N‐doped carbon nanotubes (CNTs) containing CoSe₂ nanocrystals at each node (denoted as N‐CNT/rGO/CoSe₂ NF) are designed as anodes for high‐rate sodium‐ion batteries (SIBs). Bamboo‐like N‐doped CNTs (N‐CNTs) are successfully generated on the rGO matrixed nanofiber surface, between rGO sheets and mesopores, and interconnected chemically with homogeneously distributed rGO sheets. The defects in the N‐CNTs formed by a simple etching process allow the complete phase conversion of Co into CoSe₂ through the efficient penetration of H₂Se gas inside the CNT walls. The N‐CNTs bridge the vertical defects for electron transfer in the rGO sheet layers and increase the distance between the rGO sheets during cycles. The discharge capacity of N‐CNT/rGO/CoSe₂ NF after the 10 000th cycle at an extremely high current density of 10 A g^?1 is 264 mA h g^?1, and the capacity retention measured at the 100th cycle is 89%. N‐CNT/rGO/CoSe₂ NF has final discharge capacities of 395, 363, 328, 304, 283, 263, 246, 223, 197, 171, and 151 mA h g^?1 at current densities of 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, and 20 A g^?1, respectively.     

A High‐Energy‐Density Hybrid Supercapacitor with P‐Ni(OH)2@Co(OH)2 Core–Shell Heterostructure and Fe2O3 Nanoneedle Arrays as Advanced Integrated Electrodes

Transition metal hydro/oxides (TMH/Os) are treated as the most promising alternative supercapacitor electrodes thanks to their high theoretical capacitance due to the various oxidation states and abundant cheap resources of TMH/Os. However, the poor conductivity and logy reaction kinetics of TMH/Os severely restrict their practical application. Herein, hierarchical core–shell P‐Ni(OH)₂@Co(OH)₂ micro/nanostructures are in situ grown on conductive Ni foam (P‐Ni(OH)₂@Co(OH)₂/NF) through a facile stepwise hydrothermal process. The unique heterostructure composed of P‐Ni(OH)₂ rods and Co(OH)₂ nanoflakes boost the charge transportation and provide abundant active sites when used as the intergrated cathode for supercapacitors. It delivers an ultrahigh areal specific capacitance of 4.4 C cm^?2 at 1 mA cm^?2 and the capacitance can maintain 91% after 10 000 cycles, showing an ultralong cycle life. Additionally, a hybrid supercapacitor composed with P‐Ni(OH)₂@Co(OH)₂/NF cathode and Fe₂O₃/CC anode shows a wider voltage window of 1.6 V, a remarkable energy density of 0.21 mWh cm^?2 at the power density of 0.8 mW cm^?2, and outstanding cycling stability with about 81% capacitance retention after 5000 cycles. This innovative study not only supplies a newfashioned electronic apparatus with high‐energy density and cycling stability but offers a fresh reference and enlightenment for synthesizing advanced integrated electrodes for high‐performance hybrid supercapacitors.     

A General Strategy to Glassy M-Te (M = Ru,Rh, Ir) Porous Nanorods for Efficient Electrochemical N2 Fixation

Electrochemical conversion of nitrogen (N₂) into value-added ammonia (NH₃) is highly desirable yet formidably challenging due to the extreme inertness of the N₂ molecule, which makes the development of a robust electrocatalyst prerequisite. Herein, a new class of bullet-like M-Te (M = Ru, Rh, Ir) glassy porous nanorods (PNRs) is reported as excellent electrocatalysts for N₂ reduction reaction (NRR). The optimized IrTe₄ PNRs present superior activity with the highest NH₃ yield rate (51.1 µg h⁻¹ mg⁻¹_cat.) and Faraday efficiency (15.3%), as well as long-term stability of up to 20 consecutive cycles, making them among the most active NRR electrocatalysts reported to date. Both the N₂ temperature-programmed desorption and valence band X-ray photoelectron spectroscopy data show that the strong chemical adsorption of N₂ is the key for enhancing the NRR and suppressing the hydrogen evolution reaction of IrTe₄ PNRs. Density functional theory calculations comprehensively identify that the superior adsorption strength of IrTe₄ adsorptions originates from the synergistic collaboration between electron-rich Ir and the highly electroactive surrounding Te atoms. The optimal adsorption of both N₂ and H₂O in alkaline media guarantees the superior consecutive NRR process. This work opens a new avenue for designing high-performance NRR electrocatalysts based on glassy materials.     

Achieving a Record‐High Yield Rate of 120.9 for N2 Electrochemical Reduction over Ru Single‐Atom Catalysts

The electrochemical reduction of N₂ into NH₃ production under ambient conditions represents an attractive prospect for the fixation of N₂. However, this process suffers from low yield rate of NH₃ over reported electrocatalysts. In this work, a record‐high activity for N₂ electrochemical reduction over Ru single atoms distributed on nitrogen‐doped carbon (Ru SAs/N‐C) is reported. At ?0.2 V versus reversible hydrogen electrode, Ru SAs/N‐C achieves a Faradaic efficiency of 29.6% for NH₃ production with partial current density of ?0.13 mA cm^?2. Notably, the yield rate of Ru SAs/N‐C reaches 120.9 , which is one order of magnitude higher than the highest value ever reported. This work not only develops a superior electrocatalyst for NH₃ production, but also provides a guideline for the rational design of highly active and robust single‐atom catalysts.     

Room‐Temperature Synthetic Pathways to Barium Titanate Nanocrystals

Novel room‐temperature pathways to BaTiO₃ nanocrystals have been recently developed, which stand in contrast to traditional high‐temperature methods. Peptide‐assisted, bio‐facilitated routes have been developed for low‐temperature nanocrystal growth, in addition to two low‐temperature routes completely independent of biomolecules. These innovative methods lay the groundwork for the facile production of nanoscale BaTiO₃ in economical and energy‐efficient ways.     

Low‐Noise and Large‐Linear‐Dynamic‐Range Photodetectors Based on Hybrid‐Perovskite Thin‐Single‐Crystals

Organic–inorganic halide perovskites are promising photodetector materials due to their strong absorption, large carrier mobility, and easily tunable bandgap. Up to now, perovskite photodetectors are mainly based on polycrystalline thin films, which have some undesired properties such as large defective grain boundaries hindering the further improvement of the detector performance. Here, perovskite thin‐single‐crystal (TSC) photodetectors are fabricated with a vertical p–i–n structure. Due to the absence of grain‐boundaries, the trap densities of TSCs are 10–100 folds lower than that of polycrystalline thin films. The photodetectors based on CH₃NH₃PbBr₃ and CH₃NH₃PbI₃ TSCs show low noise of 1–2 fA Hz^?1/2, yielding a high specific detectivity of 1.5 × 10¹³ cm Hz^1/2 W^?1. The absence of grain boundaries reduces charge recombination and enables a linear response under strong light, superior to polycrystalline photodetectors. The CH₃NH₃PbBr₃ photodetectors show a linear response to green light from 0.35 pW cm^?2 to 2.1 W cm^?2, corresponding to a linear dynamic range of 256 dB.     

3D Nitrogen‐Anion‐Decorated Nickel Sulfides for Highly Efficient Overall Water Splitting

Developing non‐noble‐metal electrocatalysts with high activity and low cost for both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is of paramount importance for improving the generation of H₂ fuel by electrocatalytic water‐splitting. This study puts forward a new N‐anion‐decorated Ni₃S₂ material synthesized by a simple one‐step calcination route, acting as a superior bifunctional electrocatalyst for the OER/HER for the first time. The introduction of N anions significantly modifies the morphology and electronic structure of Ni₃S₂, bringing high surface active sites exposure, enhanced electrical conductivity, optimal HER Gibbs free‐energy (ΔG_H*), and water adsorption energy change (ΔG_H2O*). Remarkably, the obtained N‐Ni₃S₂/NF 3D electrode exhibits extremely low overpotentials of 330 and 110 mV to reach a current density of 100 and 10 mA cm^?2 for the OER and HER in 1.0 m KOH, respectively. Moreover, an overall water‐splitting device comprising this electrode delivers a current density of 10 mA cm^?2 at a very low cell voltage of 1.48 V. Our finding introduces a new way to design advanced bifunctional catalysts for water splitting.     

Nitrogen Vacancies on 2D Layered W2N3: A Stable and Efficient Active Site for Nitrogen Reduction Reaction

Electrochemical nitrogen reduction reaction (NRR) under ambient conditions provides an avenue to produce carbon‐free hydrogen carriers. However, the selectivity and activity of NRR are still hindered by the sluggish reaction kinetics. Nitrogen Vacancies on transition metal nitrides are considered as one of the most ideal active sites for NRR by virtue of their unique vacancy properties such as appropriate adsorption energy to dinitrogen molecule. However, their catalytic performance is usually limited by the unstable feature. Herein, a new 2D layered W₂N₃ nanosheet is prepared and the nitrogen vacancies are demonstrated to be active for electrochemical NRR with a steady ammonia production rate of 11.66 ± 0.98 µg h^?1 mg_cata^?1 (3.80 ± 0.32 × 10^?11 mol cm^?2 s^?1) and Faradaic efficiency of 11.67 ± 0.93% at ?0.2 V versus reversible hydrogen electrode for 12 cycles (24 h). A series of ex situ synchrotron‐based characterizations prove that the nitrogen vacancies on 2D W₂N₃ are stable by virtue of the high valence state of tungsten atoms and 2D confinement effect. Density function theory calculations suggest that nitrogen vacancies on W₂N₃ can provide an electron‐deficient environment which not only facilitates nitrogen adsorption, but also lowers the thermodynamic limiting potential of NRR.     

Ultrafast Formation of Amorphous Bimetallic Hydroxide Films on 3D Conductive Sulfide Nanoarrays for Large‐Current‐Density Oxygen Evolution Electrocatalysis

Developing nonprecious oxygen evolution electrocatalysts that can work well at large current densities is of primary importance in a viable water‐splitting technology. Herein, a facile ultrafast (5 s) synthetic approach is reported that produces a novel, efficient, non‐noble metal oxygen‐evolution nano‐electrocatalyst that is composed of amorphous Ni–Fe bimetallic hydroxide film‐coated, nickel foam (NF)‐supported, Ni₃S₂ nanosheet arrays. The composite nanomaterial (denoted as Ni‐Fe‐OH@Ni₃S₂/NF) shows highly efficient electrocatalytic activity toward oxygen evolution reaction (OER) at large current densities, even in the order of 1000 mA cm^?2. Ni‐Fe‐OH@Ni₃S₂/NF also gives an excellent catalytic stability toward OER both in 1 m KOH solution and in 30 wt% KOH solution. Further experimental results indicate that the effective integration of high catalytic reactivity, high structural stability, and high electronic conductivity into a single material system makes Ni‐Fe‐OH@Ni₃S₂/NF a remarkable catalytic ability for OER at large current densities.     

A Cost‐Efficient Bifunctional Ultrathin Nanosheets Array for Electrochemical Overall Water Splitting

The design of cost‐efficient earth‐abundant catalysts with superior performance for the electrochemical water splitting is highly desirable. Herein, a general strategy for fabricating superior bifunctional water splitting electrodes is reported, where cost‐efficient earth‐abundant ultrathin Ni‐based nanosheets arrays are directly grown on nickel foam (NF). The newly created Ni‐based nanosheets@NF exhibit unique features of ultrathin building block, 3D hierarchical structure, and alloy effect with the optimized Ni₅Fe layered double hydroxide@NF (Ni₅Fe LDH@NF) exhibiting low overpotentials of 210 and 133 mV toward both oxygen evolution reaction and hydrogen evolution reaction at 10 mA cm^?2 in alkaline condition, respectively. More significantly, when applying as the bifunctional overall water splitting electrocatalyst, the Ni₅Fe LDH@NF shows an appealing potential of 1.59 V at 10 mA cm^?2 and also superior durability at the very high current density of 50 mA cm^?2.