Using tetrahexahedral gold nanorods as a heterogeneous electrocatalyst, an electrocatalytic N reduction reaction is shown to be possible at room temperature and atmospheric pressure, with a high Faradic efficiency up to 4.02% at -0.2 V vs reversible hydrogen electrode (1.648 µg h cm and 0.102 µg h cm for NH and N H ·H O, respectively).

As the NN bond in N is one of the strongest bonds in chemistry, the fixation of N 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 H and energy are largely derived from fossil fuels and thus result in large amount of CO emission. In this paper, it is demonstrated that by using Au sub-nanoclusters (≈0.5 nm ) embedded on TiO (Au loading is 1.542 wt%), the electrocatalytic N reduction reaction (NRR) is indeed possible at ambient condition. Unexpectedly, NRR with very high and stable production yield (NH : 21.4 µg h mg , 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 N 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.

Ammonia synthesis is one of the most kinetically complex and energetically challenging chemical processes in industry and has used the Harber-Bosch catalyst for over a century, which is processed under both harsh pressure (150-350 atm) and hightemperature (623-823 K), wherein the energy and capital intensive Harber-Bosch process has a huge energy cost accounting for about 1%-3% of human's energy consumption. Therefore, there has been a rough and vigorous exploration to find an environmentally benign alternative process. As the amorphous material is in a metastable state and has many "dangling bonds", it is more active than the crystallized one. In this paper, CeO -induced amorphization of Au nanoparticles anchored on reduced graphite oxide (a-Au/CeO -RGO) has been achieved by a facile coreduction method under ambient atmosphere. As a proof-of-concept experiment, a-Au/CeO -RGO hybrid catalyst containing the low noble metal (Au loading is 1.31 wt%) achieves a high Faradaic efficiency (10.10%) and ammonia yield (8.3 μg h mg ) at -0.2 V versus RHE, which is significantly higher than that of the crystalline counterpart (c-Au/RGO), and even comparable to the yields and efficiencies under harsh temperatures and/or pressures.

by mankind are invested and more than 300 million metric tons of CO 2 are generated annually. [4,5] Therefore, it is of imperative importance to reroute conventional N 2 fixation technologies and break the link between NH 3 producing and fossil fuels consuming. In response, N 2 fixation has triggered a worldwide "gold rush" and tremendous studies have been carried out recently. [6][7][8][9][10][11][12] As proposed approaches for N 2 fixation under milder conditions, using electricity to drive the NH 3 production reaction has become a good choice, [10] which represents a very attractive prospect for sustainable agriculture and achieves N 2 / NH 3 cycle to store and utilize energy from diffuse renewable sources. [13,14] Recently, some reports on electrochemical N 2 reduction reaction (NRR) with noble metal heterogeneous electrocatalysts have aroused interests in computational and experimental studies. [15][16][17] Although the suggested noble metal heterogeneous catalysts are optimally energetically efficient for NRR, their NRR catalytic activity cannot be fully demonstrated, because hydrogen evolution reaction (HER) dominates on these metals. [15][16][17] Additionally, the high costs and low abundance greatly restrict noble metal catalysts large-scale applications. To address these thorny problems, introducing transition metals with the noble ones to form polymetallic catalysts may reduce the amount of noble metal as well as improve the catalytic performance. [18][19][20] Actually, previous reports have demonstrated ternary materials can exhibit excellent performance for energy storage and conversion, such as oxygen reduction reaction, [21] oxygen evolution reaction, [22] sodium storage, [23] and so on. Therefore, the combination will be an effective means of extending the transition element properties and tuning the noble metal peculiarities. [24,25] To address this critical while daunting issue, as a proof-ofconcept experiment, taking Pd-Cu bimetallic alloys as examples, we propose and demonstrate that, by tuning the bimetallic mole ratios, NRR is indeed possible even at room temperature and atmospheric pressure. In order to enhance metallic utilization and prevent alloying nanoparticles (NPs) aggregation, 2D graphene sheets are also introduced for a good dispersion of alloys NPs. Herein, ultrafine Pd x Cu 1−x amorphous nanoclusters on reduced graphene oxide (rGO) were synthesized through a facile method. Taking prepared composites as electrochemical NRR catalysts, the optimal Pd 0.2 Cu 0.8 /rGO exhibits a yield of As an alternative approach for N 2 fixation under milder conditions, electrocatalytic nitrogen reduction reaction (NRR) represents a very attractive strategy for sustainable development and N 2 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 ancho...

The electrochemical N2 fixation, which is far from practical application in aqueous solution under ambient conditions, is extremely challenging and requires a rational design of electrocatalytic centers. We observed that bismuth (Bi) might be a promising candidate for this task because of its weak binding with H adatoms, which increases the selectivity and production rate. Furthermore, we successfully synthesized defect‐rich Bi nanoplates as an efficient noble‐metal‐free N2 reduction electrocatalyst via a low‐temperature plasma bombardment approach. When exclusively using 1H NMR measurements with N2 gas as a quantitative testing method, the defect‐rich Bi(110) nanoplates achieved a 15NH3 production rate of 5.453 μg mgBi−1 h−1 and a Faradaic efficiency of 11.68 % at −0.6 V vs. RHE in aqueous solution at ambient conditions.

Surface atomic arrangement and coordination of photocatalysts highly exposed to different crystal facets significantly affect the photoreactivity. However, controversies on the true photoreactivity of a specific facet in heterogeneous photocatalysis still exits. Herein, we exemplified well‐defined BiOBr nanosheets dominating with respective facets, (001) and (010), to track the reactivity of crystal facets for photocatalytic water splitting. The real photoreactivity of BiOBr‐(001) were evidenced to be significantly higher than BiOBr‐(010) for both hydrogen production and oxygen evolution reactions. Further in situ photochemical probing studies verified the distinct reactivity is not only owing to the highly exposed facets, but dominated by the co‐exposing facets, leading to an efficient spatial separation of photogenerated charges and further making the oxidation and reduction reactions separately occur with different reaction rates, which ordains the fate of the true photoreactivity.

Lead‐free inorganic halide perovskites have triggered appealing interests in various energy‐related applications including solar cells and photocatalysis. However, why perovskite‐structured materials exhibit excellent photoelectric properties and how the unique crystalline structures affect the charge behaviors are still not well elucidated but essentially desired. Herein, taking inorganic halide perovskite Cs3Bi2Br9 as a prototype, the significant derivation process of silver atoms incorporation to induce the structural transformation from Cs3Bi2Br9 to Cs2AgBiBr6, which brings about dramatic differences in photoelectric properties is unraveled. It is demonstrated that the silver incorporation results in the co‐operated orbitals hybridization, which makes the electronic distributions in conduction and valence bands of Cs2AgBiBr6 more dispersible, eliminating the strong localization of electron–hole pairs. As consequences of the electronic structures derivation, exhilarating changes in photoelectric properties like band structure, exciton binding energy, and charge carrier dynamics are verified experimentally and theoretically. Using photocatalytic hydrogen evolution activity under visible light as a typical evaluation, such crystalline structure transformation contributes to a more than 100‐fold enhancement in photocatalytic performances compared with pristine Cs3Bi2Br9, verifying the significant effect of structural derivations on the exhibited performances. The findings will provide evidences for understanding the origin of photoelectric properties for perovskites semiconductors in solar energy conversion.

Based on a rechargeable lithium-nitrogen battery, an advanced strategy for reversible nitrogen fixation and energy conversion has been successfully implemented at room temperature and atmospheric pressure. It shows a promising nitrogen fixation faradic efficiency and superior cyclability. SUMMARYAlthough the availability of nitrogen (N 2 ) from the atmosphere for N 2 fixation is limitless, it is immensely challenging to artificially fix N 2 at ambient temperature and pressure given the element's chemical inertness and stability. In this article, as a proof-of-concept experiment, we report on the successful implementation of a reversible N 2 cycle based on a rechargeable lithium-nitrogen (Li-N 2 ) battery with the proposed reversible reaction of 6Li + N 2 ! 2Li 3 N. The assembled N 2 fixation battery system, consisting of a Li anode, ether-based electrolyte, and a carbon cloth cathode, shows a promising electrochemical faradic efficiency (59%). The unique properties of Li-N 2 rechargeable batteries not only provide promising candidates for N 2 fixation but also enable an advanced N 2 /Li 3 N cycle strategy for next-generation electrochemical energy-storage systems.