Abstract Most current research is devoted to electrochemical nitrate reduction reaction for ammonia synthesis under alkaline/neutral media while the investigation of nitrate reduction under acidic conditions is rarely reported. In this work, we demonstrate the potential of TiO 2 nanosheet with intrinsically poor hydrogen-evolution activity for selective and rapid nitrate reduction to ammonia under acidic conditions. Hybridized with iron phthalocyanine, the resulting catalyst displays remarkably improved efficiency toward ammonia formation owing to the enhanced nitrate adsorption, suppressed hydrogen evolution and lowered energy barrier for the rate-determining step. Then, an alkaline-acid hybrid Zn-nitrate battery was developed with high open-circuit voltage of 1.99 V and power density of 91.4 mW cm –2 . Further, the environmental sulfur recovery can be powered by above hybrid battery and the hydrazine-nitrate fuel cell can be developed for simultaneously hydrazine/nitrate conversion and electricity generation. This work demonstrates the attractive potential of acidic nitrate reduction for ammonia electrosynthesis and broadens the field of energy conversion. 

Electrochemical nitrate reduction in acid enables high-efficiency ammonia synthesis and high-voltage pollutes-based fuel cells

The shipping industry has reached a higher level of maturity in terms of its knowledge and awareness of decarbonization challenges. Carbon-free or carbon-neutralized green fuel, such as green hydrogen, green ammonia, and green methanol, are being widely discussed. However, little attention has paid to the green fuel pathway from renewable energy to shipping. This paper, therefore, provides a review of the production methods for green power (green hydrogen, green ammonia, and green methanol) and analyzes the potential of green fuel for application to shipping. The review shows that the potential production methods for green hydrogen, green ammonia, and green methanol for the shipping industry are (1) hydrogen production from seawater electrolysis using green power; (2) ammonia production from green hydrogen + Haber–Bosch process; and (3) methanol production from CO2 using green power. While the future of green fuel is bright, in the short term, the costs are expected to be higher than conventional fuel. Our recommendations are therefore as follows: improve green power production technology to reduce the production cost; develop electrochemical fuel production technology to increase the efficiency of green fuel production; and explore new technology. Strengthening the research and development of renewable energy and green fuel production technology and expanding fuel production capacity to ensure an adequate supply of low- and zero-emission marine fuel are important factors to achieve carbon reduction in shipping.

/pdf/a-prompt-decarbonization-pathway-for-shipping-green-hydrogen-2cpjyifn.pdf

A Prompt Decarbonization Pathway for Shipping: Green Hydrogen, Ammonia, and Methanol Production and Utilization in Marine Engines

Zn-NO3− batteries can generate electricity while environmentally friendly producing NH3, making them a very promising device. However, the conversion of NO3− to NH3 involves a proton-assisted 8-electron (8e–) transfer process...

Electrocatalytic nitrate-to-ammonia conversion on CoO/CuO nanoarray through Zn-nitrate battery

Engineering active sites of cathodic materials for high-performance Zn-nitrogen batteries

Nitrate with its high stability and persistence in water can pose a serious threat to both human health and aquatic ecosystems. To tackle this issue, the electrochemical nitrate reduction reaction (NO3RR) is considered the most effective solution for reducing excess nitrate (NO3–) in water and wastewater, into a value-added product ammonia (NH3). The efficiency of NO3– removal during the electrochemical reduction process is directly influenced by the genuine catalysts, enable them one of the most crucial factors. The objective of this review is to elucidate the function of copper-based catalysts in the electrochemical conversion of NO3– to NH3 and to identify the factors that affect the performance of these catalysts. We have also devised strategies that can be applied to enhance catalytic efficiency, along with offering an overview of the recent advancements achieved in the design of copper-based electrocatalysts. This comprehensive review will provide a detailed insight into the role of Cu-based materials in electrochemical NO3– reduction and the advancement of effective electrode materials for the intended reactions. 

Recent Developments in Designing Cu-Based Electrocatalysts and Advanced Strategies for Electrochemical Nitrate Reduction to Ammonia

Since the conventional Haber-Bosch ammonia synthesis loop suffers from harsh process conditions, high energy consumption, and heavy pollution, the artificial catalytic synthetic NH3 has emerged as a promising alternative method for producing NH3. Meanwhile, nitrate (NO3–) accumulation in the environment causes serious problems involving health and environmental issues. The urgent need to eliminate NO3– and produce NH3 perfectly caters to the NO3– reduction reaction (NO3RR) via an attractive electrocatalytic route. Cu-based catalysts exhibit an inhibiting effect on hydrogen evolution, rapid reduction kinetics, and stable catalytic performance, revealing remarkable advantages for NO3RR. In this review, we summarize the recent achievements of Cu-based catalysts in electrocatalytic NO3RR, discuss the detection methods for evaluating NO3RR performance, and introduce the fundamentals for understanding the thermodynamics and kinetics. This review can provide guidance and help for the rational design and development of non-noble metal catalysts in electrocatalytic NO3RR to NH3. 

Research Progress on Cu-Based Catalysts for Electrochemical Nitrate Reduction Reaction to Ammonia

Electrochemical ammonia synthesis via nitrate reduction reaction (NO3RR) under ambient condition is increasingly recognized as a sustainable alternative to the conventional Haber-Bosch process. Transition metal phosphides have attracted extensive attention as promising electrocatalysts owing to their unique proton provision. However, a challenge persists as the protons tend to dimerize to form H2 through the hydrogen evolution reaction (HER). In this work, we manipulate the proton preference in a Ni-Co bimetallic phosphide through vacancy engineering, leading to a notable enhancement in NH3 production. The developed NiCoP-VP with electron-rich surface demonstrates high selectivity, faradaic efficiency, and yield rate for ammonia, achieving a maximum yield rate of 16.63 mgNH3 h−1 cm−2 (ca. 83.17 mgNH3 h−1 mgcat.−1) at − 0.7 V vs. RHE. Density functional theory calculation reveal an increased energy barrier for proton dimerization and a more favorable rate-determining protonation step of *NO in NO3RR. Furthermore, a Zn-NO3− battery system was constructed based on NiCoP-VP, which showed dual functionality of generating electricity and producing NH3. With an open circuit voltage of 1.39 V and a peak-power density of 1.14 mW cm−2, the battery system presents a promising application for sustainable energy supply and green NH3 synthesis. 

Vacancy enhanced proton preference in bimetallic phosphide catalysts for electrochemical ammonia synthesis and energy supply in Zn-NO3− battery

Manganese oxides (MnOx) have been emerged as highly active catalysts for the aerobic oxidation of biomass-derived compounds. Herein, a facile urea–redox hydrothermal method was employed to scalable synthesis of MnOx oxides with surface abundant unsaturated Mn and O species. The defective MnOx (MnOx–D) catalyst exhibited remarkable catalytic performance, enabling the room-temperature aerobic oxidation of biomass–derived alcohols with yields exceeding 99%. This represents a substantial 90.8-fold increase in activity compared to commercial MnO2. Moreover, MnOx–D demonstrated broad substrate scopes for various biomass–derived alcohols and displayed recyclability for the aerobic oxidative conversion of 5-hydroxymethylfurfural (HMF) over five cycles. Through a comprehensive analysis involving X–ray photoelectron spectroscopy (XPS), in–situ infrared (IR) spectroscopy, and controlled experiments, it was established that the presence of surface–adsorbed H2O species on MnOx–D catalyst significantly influences its catalytic performance. Mechanism studies revealed that the aerobic oxidation of biomass–derived R–CH2–OH compounds into the corresponding aldehydes can proceed via radical and non–radical pathways. Notably, the catalytic activity of MnOx–D catalyst in both pathways is mediated by the surface adsorbed H2O species. In the radical route, surface adsorbed H2O and O2 species are converted into active •OH radical species, while in the non–radical route, surface adsorbed H2O can form a complex of HMF––H2O species. Both processes enhance the abstraction of H from the O–H and C–H bonds in the R–CH2–OH compounds on MnOx–D catalyst. This discovery could potentially guide the development of efficient metal oxidic catalysts for the oxidation of biomass–derived R–CH2–OH compounds 

Surface adsorbed–H2O promoted aerobic oxidation of biomass–derived alcohols on MnO catalysts

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Research Progress on Cu-Based Catalysts for Electrochemical Nitrate Reduction Reaction to Ammonia

Vacancy enhanced proton preference in bimetallic phosphide catalysts for electrochemical ammonia synthesis and energy supply in Zn-NO3− battery

Surface adsorbed–H2O promoted aerobic oxidation of biomass–derived alcohols on MnO catalysts