The electrochemical method of combining N2 and H2O to produce ammonia (i.e., the electrochemical nitrogen reduction reaction E‐NRR) continues to draw attention as it is both environmentally friendly ...and well suited for a progressively distributed farm economy. Despite the multitude of recent works on the E‐NRR, further progress in this field faces a bottleneck. On the one hand, despite the extensive exploration and trial‐and‐error evaluation of E‐NRR catalysts, no study has stood out to become the stage protagonist. On the other hand, the current level of ammonia production (microgram‐scale) is an almost insurmountable obstacle for its qualitative and quantitative determination, hindering the discrimination between true activity and contamination. Herein i) the popular theory and mechanism of the NRR are introduced; ii) a comprehensive summary of the recent progress in the field of the E‐NRR and related catalysts is provided; iii) the operational procedures of the E‐NRR are addressed, including the acquisition of key metrics, the challenges faced, and the most suitable solutions; iv) the guiding principles and standardized recommendations for the E‐NRR are emphasized and future research directions and prospects are provided.
Ammonia represents the blood of industry; and agriculture, crop growth, green energy fuels, and industry production are inseparable from it. The electrochemical synthesis of ammonia is expected to replace the harsh and environmentally unfriendly Harber–Bosch process. A timely and comprehensive review of the booming ambient electrochemical ammonia synthesis is presented to promote its rapid and healthy development.
Electrocatalytic nitrogen fixation is considered a promising approach to achieve NH3 production. However, due to the chemical inertness of nitrogen, it is necessary to develop efficient catalysts to ...facilitate the process of nitrogen reduction. Here, molybdenum carbide nanodots embedded in ultrathin carbon nanosheets (Mo2C/C) are developed to serve as a catalyst candidate for highly efficient and robust N2 fixation through an electrocatalytic nitrogen reduction reaction (NRR). The as‐synthesized Mo2C/C nanosheets show excellent catalytic performance with a high NH3 yield rate (11.3 µg h−1 mg−1
Mo2C) and Faradic efficiency (7.8%) for NRR under ambient conditions. More importantly, the isotopic experiments using 15N2 as a nitrogen source confirm that the synthesized ammonia is derived from the direct supply of nitrogen. This result also demonstrates the possibility of high‐efficiency nitrogen reduction even though accompanied with vigorous hydrogen evolution.
An effective size‐control synthesis strategy is proposed to endow the nitrogen reduction reaction (NRR) performance of Mo2C nanodots by boosting nitrogen adsorption and activation. The Mo2C nanodots show excellent NRR catalytic performance with a high NH3 yield rate (11.3 µg h−1 mg−1
Mo2C) under ambient conditions. This result demonstrates the possibility of high‐efficiency nitrogen reduction even though accompanied with vigorous hydrogen evolution.
Constructing efficient catalysts for the N2 reduction reaction (NRR) is a major challenge for artificial nitrogen fixation under ambient conditions. Herein, inspired by the principle of “like ...dissolves like”, it is demonstrated that a member of the nitrogen family, well‐exfoliated few‐layer black phosphorus nanosheets (FL‐BP NSs), can be used as an efficient nonmetallic catalyst for electrochemical nitrogen reduction. The catalyst can achieve a high ammonia yield of 31.37 μg h−1 mg−1cat. under ambient conditions. Density functional theory calculations reveal that the active orbital and electrons of zigzag and diff‐zigzag type edges of FL‐BP NSs enable selective electrocatalysis of N2 to NH3 via an alternating hydrogenation pathway. This work proves the feasibility of using a nonmetallic simple substance as a nitrogen‐fixing catalyst and thus opening a new avenue towards the development of more efficient metal‐free catalysts.
Well‐exfoliated few‐layer black phosphorus nanosheets (FL‐BP NSs) were developed as an efficient nonmetallic catalyst for electrochemical nitrogen reduction. The catalyst can achieve a high ammonia yield of 31.37 μg h−1 mg−1cat. under ambient conditions. DFT calculations show that the zigzag and diff‐zigzag edges of the FL‐BP NSs are the active centers, which enable selective electroreduction of N2 to NH3 via an alternating hydrogenation pathway.
Hydrogen peroxide (H2O2) is an environment‐friendly and efficient oxidant with a wide range of applications in different industries. Recently, the production of hydrogen peroxide through direct ...electrosynthesis has attracted widespread research attention, and has emerged as the most promising method to replace the traditional energy‐intensive multi‐step anthraquinone process. In ongoing efforts to achieve highly efficient large‐scale electrosynthesis of H2O2, carbon‐based materials have been developed as 2e− oxygen reduction reaction catalysts, with the benefits of low cost, abundant availability, and optimal performance. This review comprehensively introduces the strategies for optimizing carbon‐based materials toward H2O2 production, and the latest advances in carbon‐based hybrid catalysts. The active sites of the carbon‐based materials and the influence of coordination heteroatom doping on the selectivity of H2O2 are extensively analyzed. In particular, the appropriate design of functional groups and understanding the effect of the electrolyte pH are expected to further improve the selective efficiency of producing H2O2 via the oxygen reduction reaction. Methods for improving catalytic activity by interface engineering and reaction kinetics are summarized. Finally, the challenges carbon‐based catalysts face before they can be employed for commercial‐scale H2O2 production are identified, and prospects for designing novel electrochemical reactors are proposed.
The latest advances in carbon‐based hybrid catalysts toward hydrogen peroxide (H2O2) production are reviewed. In particular, the design of functional groups and the dependence of electrolyte pH play important roles to further improve the selectivity of H2O2 production via the oxygen reduction reaction.
The purpose of this paper is to develop a compromise-typed variable weight decision method for solving hybrid multiattribute decision making problems with multiple types of attribute values. The ...compromise-typed variable weight functions are defined and constructed by utility functions. Moreover, the variable weight synthesis and the orness measures based on the coefficients of absolute risk aversion are analyzed in variable weight decision making. The comprehensive values of alternatives based on the compromise-typed variable weight decision method are calculated. The decision-making results are determined according to the comprehensive values. Finally, an example and a detailed comparison analysis are presented to show the applicability and validity of the proposed method.
Lead halide perovskites have emerged as promising semiconducting materials for different applications owing to their superior optoelectronic properties. Although the community holds different views ...toward the toxic lead in these high‐performance perovskites, it is certainly preferred to replace lead with nontoxic, or at least less‐toxic, elements while maintaining the superior properties. Here, the design rules for lead‐free perovskite materials with structural dimensions from 3D to 0D are presented. Recent progress in lead‐free halide perovskites is reviewed, and the relationships between the structures and fundamental properties are summarized, including optical, electric, and magnetic‐related properties. 3D perovskites, especially A2B+B3+X6‐type double perovskites, demonstrate very promising optoelectronic prospects, while low‐dimensional perovskites show rich structural diversity, resulting in abundant properties for optical, electric, magnetic, and multifunctional applications. Furthermore, based on these structure–property relationships, strategies for multifunctional perovskite design are proposed. The challenges and future directions of lead‐free perovskite applications are also highlighted, with emphasis on materials development and device fabrication. The research on lead‐free halide perovskites at Linköping University has benefited from inspirational discussions with Prof. Olle Inganäs.
The development of lead‐free perovskites has attracted increasing attention. The design rules for lead‐free perovskite materials with diverse structures are presented. The structure–property relationships and optical‐, electric‐, and magnetic‐related applications of these lead‐free perovskites are summarized. Based on these structure–property relationships, strategies for multifunctional perovskite design are proposed.
Cu-exchanged small-pore zeolites have been extensively studied in the past decade as state-of-the-art selective catalytic reduction (SCR) catalysts for diesel engine exhaust NOx abatement for the ...transportation industry. During this time, Fe-exchanged small-pore zeolites, e.g., Fe/SSZ-13, Fe/SAPO-34, Fe/SSZ-39 and high-silica Fe/LTA, have also been investigated but much less extensively. In comparison to their Cu-exchanged counterparts, such Fe/zeolite catalysts display inferior low-temperature activities, but improved stability and high-temperature SCR selectivities. Such characteristics entitle these catalysts to be considered as key components of highly efficient emission control systems to improve the overall catalyst performance. In this short review, recent studies on Fe-exchanged small-pore zeolite SCR catalysts are summarized, including (1) the synthesis of small-pore Fe/zeolites; (2) nature of the SCR active Fe species in these catalysts as determined by experimental and theoretical approaches, including Fe species transformation during hydrothermal aging; (3) SCR reactions and structure-function correlations; and (4) a few aspects on industrial applications.
Development of easy‐to‐make, highly active, and stable bifunctional electrocatalysts for water splitting is important for future renewable energy systems. Three‐dimension (3D) porous Ni/Ni8P3 and ...Ni/Ni9S8 electrodes are prepared by sequential treatment of commercial Ni‐foam with acid activation, followed by phosphorization or sulfurization. The resultant materials can act as self‐supported bifunctional electrocatalytic electrodes for direct water splitting with excellent activity toward oxygen evolution reaction and hydrogen evolution reaction in alkaline media. Stable performance can be maintained for at least 24 h, illustrating their versatile and practical nature for clean energy generation. Furthermore, an advanced water electrolyzer through exploiting Ni/Ni8P3 as both anode and cathode is fabricated, which requires a cell voltage of 1.61 V to deliver a 10 mA cm−2 water splitting current density in 1.0 m KOH solution. This performance is significantly better than that of the noble metal benchmark—integrated Ni/IrO2 and Ni/Pt–C electrodes. Therefore, these bifunctional electrodes have significant potential for realistic large‐scale production of hydrogen as a replacement clean fuel to polluting and limited fossil‐fuels.
Three‐dimension nickel‐based electrocatalytic electrodes (Ni/Ni8P3 and Ni/Ni9S8) are developed for application in water splitting. The as‐obtained Ni/Ni8P3 catalytic electrode, particularly exhibiting excellent electrocatalytic activity and stability due to its advanced structure effects, can serve as a highly efficient and stable bifunctional catalyst for overall water splitting.
The aqueous electrocatalytic reduction of NO3− into NH3 (NitrRR) presents a sustainable route applicable to NH3 production and potentially energy storage. However, the NitrRR involves a directly ...eight‐electron transfer process generally required a large overpotential (<−0.2 V versus reversible hydrogen electrode (vs. RHE)) to reach optimal efficiency. Here, inspired by biological nitrate respiration, the NitrRR was separated into two stages along a 2+6‐electron pathway to alleviate the kinetic barrier. The system employed a Cu nanowire catalyst produces NO2− and NH3 with current efficiencies of 91.5 % and 100 %, respectively at lower overpotentials (>+0.1 vs. RHE). The high efficiency for such a reduction process was further explored in a zinc‐nitrate battery. This battery could be specified by a high output voltage of 0.70 V, an average energy density of 566.7 Wh L−1 at 10 mA cm−2 and a power density of 14.1 mW cm−2, which is well beyond all previously reported similar concepts.
For the efficient electrocatalytic conversion of NO3− to NH3, a two‐stage process following the 2+6‐electron pathway is proposed inspired by biological nitrate respiration. This system produces NO2− and NH3 at low overpotentials (>+0.1 vs. RHE), resulting in a low energy consumption of 17.7 kWh kg−1 for NH3 production and high energy density of 566.7 Wh L−1 at 10 mA cm−2 for Zn−NO3− battery.
Abstract
The one-step electrochemical synthesis of H
2
O
2
is an on-site method that reduces dependence on the energy-intensive anthraquinone process. Oxidized carbon materials have proven to be ...promising catalysts due to their low cost and facile synthetic procedures. However, the nature of the active sites is still controversial, and direct experimental evidence is presently lacking. Here, we activate a carbon material with dangling edge sites and then decorate them with targeted functional groups. We show that quinone-enriched samples exhibit high selectivity and activity with a H
2
O
2
yield ratio of up to 97.8 % at 0.75 V vs. RHE. Using density functional theory calculations, we identify the activity trends of different possible quinone functional groups in the edge and basal plane of the carbon nanostructure and determine the most active motif. Our findings provide guidelines for designing carbon-based catalysts, which have simultaneous high selectivity and activity for H
2
O
2
synthesis.
PDF
