Tandem Nitrate-to-Ammonia Conversion on Atomically Precise Silver Nanocluster/MXene Electrocatalyst.

Electrocatalytic reduction of nitrate (NO3 RR) to synthesize ammonia (NH3 ) provides a competitive manner for carbon neutrality and decentralized NH3 synthesis. Atomically precise nanoclusters, as an advantageous platform for investigating the NO3 RR mechanisms and actual active sites, remain largely underexplored due to the poor stability. Herein, we report a (NH4 )9 [Ag9 (mba)9 ] nanoclusters (Ag9 NCs) loaded on Ti3 C2 MXene (Ag9 /MXene) for highly efficient NO3 RR performance towards ambient NH3 synthesis with improved stability in neutral medium. The composite structure of MXene and Ag9 NCs enables a tandem catalysis process for nitrate reduction, significantly increasing the selectivity and FE of NH3 . Besides, compared with individual Ag9 NCs, Ag9 /MXene has better stability with the current density performed no decay after 108 hours of reaction. This work provides a strategy for improving the catalytic activity and stability of atomically precise metal NCs, expanding the mechanism research and application of metal NCs.

Unveiling Ionized Interfacial Water-Induced Localized H* Enrichment for Electrocatalytic Nitrate Reduction.

Electrocatalytic nitrate reduction reaction (NO3RR) is a process that requires the participation of eight electrons and nine protons. The regulation of active hydrogen (H*) supply and a deep understanding of related processes are necessary for improving the ammonia yield rate and Faradaic efficiency (FE). Herein, we synthesized a series of atomically precise copper-halide clusters Cu2X2(BINAP)2 (X=Cl, Br, I), among which the Cu2Cl2(BINAP)2 cluster shows the optimal ammonia FE of 94.0 % and an ammonia yield rate of 373 µmol h-1 cm-2. In situ experiments and theoretical calculations reveal that halogen atoms, especially Cl in Cu2Cl2(BIANP)2, can significantly affect the distance of alkali metal-ionized water on the catalyst surface, which can promote the water dissociation to enhance the localized H* enrichment for the continues hydrogenation of nitrate to ammonia. This work explains the role of H* in the hydrogenation process of NO3RR and the importance of localized H* enrichment strategy for improving the FEs.

Electropolymerization of Metal Clusters Establishing a Versatile Platform for Enhanced Catalysis Performance.

Atomically precise metal clusters are attractive as highly efficient catalysts, but suffer from continuous efficiency deactivation in the catalytic process. Here, we report the development of an efficient strategy that enhances catalytic performance by electropolymerization (EP) of metal clusters into hybrid materials. Based on carbazole ligand protection, three polymerized metal-cluster hybrid materials, namely Poly-Cu14 cba, Poly-Cu6 Au6 cbz and Poly-Cu6 Ag4 cbz, were prepared. Compared with isolated metal clusters, metal clusters immobilizing on a biscarbazole network after EP significantly improved their electron-transfer ability and long-term recyclability, resulting in higher catalytic performance. As a proof-of-concept, Poly-Cu14 cba was evaluated as an electrocatalyst for reducing nitrate (NO3 - ) to ammonia (NH3 ), which exhibited ≈4-fold NH3 yield rate and ≈2-fold Faraday efficiency enhancement compared to that of Cu14 cba with good durability. Similarly, Poly-Cu6 Au6 cbz showed 10 times higher photocatalytic efficiency towards chemical warfare simulants degradation than the cluster counterpart.

Stepwise structural evolution toward robust carboranealkynyl-protected copper nanocluster catalysts for nitrate electroreduction.

Atomically precise metal nanoclusters (NCs) are emerging as idealized model catalysts for imprecise metal nanoparticles to unveil their structure-activity relationship. However, the directional synthesis of robust metal NCs with accessible catalytic active sites remains a great challenge. In this work, we achieved bulky carboranealkynyl-protected copper NCs, the monomer Cu13·3PF6 and nido-carboranealkynyl bridged dimer Cu26·4PF6, with fair stability as well as accessible open metal sites step by step through external ligand shell modification and metal-core evolution. Both Cu13·3PF6 and Cu26·4PF6 demonstrate remarkable catalytic activity and selectivity in electrocatalytic nitrate (NO3-) reduction to NH3 reaction, with the dimer Cu26·4PF6 displaying superior performance. The mechanism of this catalytic reaction was elucidated through theoretical computations in conjunction with in situ FTIR spectra. This study not only provides strategies for accessing desired copper NC catalysts but also establishes a platform to uncover the structure-activity relationship of copper NCs.

Electrocatalytic Nitrate Reduction on Metallic CoNi-Terminated Catalyst with Industrial-Level Current Density in Neutral Medium.

Green ammonia synthesis through electrocatalytic nitrate reduction reaction (eNO3RR) can serve as an effective alternative to the traditional energy-intensive Haber-Bosch process. However, achieving high Faradaic efficiency (FE) at industrially relevant current density in neutral medium poses significant challenges in eNO3RR. Herein, with the guidance of theoretical calculation, a metallic CoNi-terminated catalyst is successfully designed and constructed on copper foam, which achieves an ammonia FE of up to 100% under industrial-level current density and very low overpotential (-0.15 V versus reversible hydrogen electrode) in a neutral medium. Multiple characterization results have confirmed that the maintained metal atom-terminated surface through interaction with copper atoms plays a crucial role in reducing overpotential and achieving high current density. By constructing a homemade gas stripping and absorption device, the complete conversion process for high-purity ammonium nitrate products is demonstrated, displaying the potential for practical application. This work suggests a sustainable and promising process toward directly converting nitrate-containing pollutant solutions into practical nitrogen fertilizers.

In Situ/Operando Methods for Understanding Electrocatalytic Nitrate Reduction Reaction.

With the development of industrial and agricultural, a large amount of nitrate is produced, which not only disrupts the natural nitrogen cycle, but also endangers public health. Among the commonly used nitrate treatment techniques, the electrochemical nitrate reduction reaction (eNRR) has attracted extensive attention due to its mild conditions, pollution-free nature, and other advantages. An in-depth understanding of the eNRR mechanism is the prerequisite for designing highly efficient electrocatalysts. However, some traditional characterization tools cannot comprehensively and deeply study the reaction process. It is necessary to develop in situ and operando techniques to reveal the reaction mechanism at the time-resolved and atomic level. This review discusses the eNRR mechanism and summarizes the possible in situ techniques used in eNRR. A detailed introduction of various in situ techniques and their help in understanding the reaction mechanism is provided. Finally, the current challenges and future opportunities in this research area are discussed and highlighted.

Electronically and Geometrically Modified Single-Atom Fe Sites by Adjacent Fe Nanoparticles for Enhanced Oxygen Reduction.

Fe-N-C materials exhibit excellent activity and stability for oxygen reduction reaction (ORR), as one of the most promising candidates to replace commercial Pt/C catalysts. However, it is challenging to unravel features of the superior ORR activity originating from Fe-N-C materials. In this work, the electronic and geometric structures of the isolated Fe-N-C sites and their correlations with the ORR performance are investigated by varying the secondary thermal activation temperature of a rationally designed NC-supported Fe single-atom catalyst (SAC). The systematic analyses demonstrate the significant role of coordinated atoms of SA and metallic Fe nanoparticles (NPs) in altering the electronic structure of isolated Fe-N-C sites. Meanwhile, strong interaction between isolated Fe-N-C sites and adjacent Fe NPs can change the geometric structure of isolated Fe-N-C sites. Theoretical calculations reveal that optimal regulation of the electronic and geometric structure of isolated Fe-N-C sites by the co-existence of Fe NPs narrows the energy barriers of the rate-limiting steps of ORR, resulting in outstanding ORR performance. This work not only provides the fundamental understanding of the underlying structure-activity relationship, but also sheds light on designing efficient Fe-N-C catalysts.

Pressure-Triggered Blue Emission of Zero-Dimensional Organic Bismuth Bromide Perovskite.

Understanding the structure-property relationships in Zero-dimensional (0D) organic-inorganic metal halide perovskites (OMHPs) is essential for their use in optoelectronic applications. Moreover, increasing the emission intensity, particularly for blue emission, is considerably a challenge. Here, intriguing pressure-induced emission (PIE) is successfully achieved from an initially nonluminous 0D OMHP [(C6H11NH3)4BiBr6]Br·CH3CN (Cy4BiBr7 ) upon compression. The emission intensity increases significantly, even reaching high-efficiency blue luminescence, as the external pressure is increased to 4.9 GPa. Analyses of the in situ high-pressure experiments and first-principle calculations indicate that the observed PIE can be attributed to the enhanced exciton binding energy associated with [BiBr6]3- octahedron distortion under pressure. This study of Cy4BiBr7 sheds light on the relationship between the structure and optical properties of OMHPs. The results may improve potential applications of such materials in the fields of pressure sensing and trademark security.

Hydrogenated Cagelike Titania Hollow Spherical Photocatalysts for Hydrogen Evolution under Simulated Solar Light Irradiation.

We synthesized the hydrogenated cagelike TiO2 hollow spheres through a facile sacrificial template method. After the hydrogenation treatment, the disordered surface layer and cagelike pores were generated on the shell of the hollow spheres. The spheres exhibit a high hydrogen evolution rate of 212.7 ± 10.6 µmol h(-1) (20 mg) under the simulated solar light irradiation, which is ∼12 times higher than the hydrogenated TiO2 solid spheres and is ∼9 times higher than the original TiO2 hollow spheres. The high activity results from the unique architectures and hydrogenation. Both the multiple reflection that was improved by the cagelike hollow structures and the red shift of the absorption edge that was induced by hydrogenation can enhance the ultraviolet and visible light absorption. In addition, the high concentration of oxygen vacancies, as well as the hydrogenated disordered surface layer, can improve the efficiency for migration and separation of generated charge carriers.

In Situ Formation of Disorder-Engineered TiO2(B)-Anatase Heterophase Junction for Enhanced Photocatalytic Hydrogen Evolution.

Hydrogenation of semiconductors is an efficient way to increase their photocatalytic activity by forming disorder-engineered structures. Herein, we report a facile hydrogenation process of TiO2(B) nanobelts to in situ generate TiO2(B)-anatase heterophase junction with a disordered surface shell. The catalyst exhibits an excellent performance for photocatalytic hydrogen evolution under the simulated solar light irradiation (∼580 µmol h(-1), 0.02 g photocatalyst). The atomically well-matched heterophase junction, along with the disorder-engineered surface shell, promotes the separation of electron-hole and inhibits their recombination. This strategy can be further employed to design other disorder-engineered composite photocatalysts for solar energy utilization.