Boosting Electrocatalytic Nitrate-to-Ammonia Conversion via Plasma Enhanced CuCo Alloy–Substrate Interaction

Wu, Angjian; Zhou, Yingshan; Lv, Jiabao; Zhang, De‐Long; Peng, Yaqi; Ye, Qiulin; Fu, Pengcheng; Wang, Weitao; Lin, Xiaoqing; Liu, Shaojun; Xu, Mengxia; Qi, Zhifu; Zhu, Songqiang; Zhu, Wei; Yan, Jun; Tu, Xin; Li, Xiaodong

doi:10.1021/acssuschemeng.2c04249

Cited by 26 publications

(16 citation statements)

References 51 publications

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“…Electrochemical approaches have been proposed to recover nitrogen nutrients by driving the thermodynamically favorable NO 3 – to NH 3 conversion instead of reducing it to N 2 . ,− Therefore, electrocatalytic NO 3 – reduction to NH 3 has been extensively investigated in recent work. The performances of metallic (Ti, Cu, − Co, , Ru, Ni, Fe, and Bi) and bimetallic (CuCo, CuNi, , and CuPd − ) electrocatalysts have been reported at various pH levels and NO 3 – concentrations. Deng et al (pH 14) and Kani et al (pH 7 and 14) demonstrated >90% Faradaic efficiency for NH 3 production on Co catalysts.…”

Section: Introductionmentioning

confidence: 99%

“…5,10−12 Therefore, electrocatalytic NO 3 − reduction to NH 3 has been extensively investigated in recent work. The performances of metallic (Ti, 13 Cu, 14−22 Co, 23,24 Ru, 25 Ni, 26 Fe, 27 and Bi 28 ) and bimetallic (CuCo, 29 CuNi, 30,31 and CuPd 32−34 ) electrocatalysts have been reported at various pH levels and NO 3 − concentrations. Deng et al 23 Kani et al 24 (pH 7 and 14) demonstrated >90% Faradaic efficiency for NH 3 production on Co catalysts.…”

Section: Introductionmentioning

confidence: 99%

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Combined Effects of Concentration, pH, and Polycrystalline Copper Surfaces on Electrocatalytic Nitrate-to-Ammonia Activity and Selectivity

et al. 2023

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Wastewater nitrates (NO3 –) represent an untapped source for nutrient recovery. This study explores the effects of NO3 – concentration ranging from 0.1 to 1 M and pH conditions of 8, 10, and 14 on the electrochemical reduction to ammonia (NH3) with polycrystalline Cu electrodes. Cyclic voltammograms prove pH- and concentration-dependent reaction kinetics. Chronoamperometry tests probed the reaction selectivity to NH3 production for a fixed potential across different pH conditions. The maximum NH3 Faradaic efficiency achieved was 46% ± 11% for 1 M NaNO3 at pH 14 at −0.55 V vs the reversible hydrogen electrode (RHE), while the minimum was 25% ± 6% for 1 M NaNO3 at pH 8. Distinctly, at pH 8 and 10, 0.1 M NaNO3 results in higher NH3 Faradaic efficiencies compared to the 1 M solution. Product quantification reveals that as the pH decreases, more charge is utilized for the formation of NO2 as compared to NH3 as a product. Large trial-to-trial uncertainties motivated the application of in situ electrochemical impedance spectroscopy to provide insights into the causal factors. Fitted parameters from impedance measurements correlate with measured contributions of net charge utilized for NH3 and NO2 – production. Trial-to-trial variations map with changes in both the charge-transfer resistance and the effective double-layer capacitance. Changes in surface roughness and consequently the electrochemically active surface area are more dominant for 0.1 M NaNO3 solutions, while other variations play a significant role for 1 M NaNO3 tests. Overall, these results indicate that catalytic performance of NO3 – reduction on Cu is highly sensitive to pH, concentration, secondary ions, and surface composition.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Combined Effects of Concentration, pH, and Polycrystalline Copper Surfaces on Electrocatalytic Nitrate-to-Ammonia Activity and Selectivity

et al. 2023

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“…[ 12–14 ] As nitric oxide (NO) is one of the major nitrogeneous pollutants abundant in fossil fuel combustion and other chemical industry, [ 15,16 ] the rational utilization of waste NO via electrocatalysis can simultaneously alleviate the environmental load and reverse the anthropogenically global nitrogen cycle imbalance. [ 17–19 ] For efficient electrocatalytic NO reduction reaction (NORR), the Cu‐based catalyst has been validated theoretically and experimentally. [ 20 ] Nevertheless, it still suffers from high overpotential and competitive HER, which could be optimized by further modification such as transition metal (oxide) deposition.…”

Section: Introductionmentioning

confidence: 99%

“…global nitrogen cycle imbalance. [17][18][19] For efficient electrocatalytic NO reduction reaction (NORR), the Cu-based catalyst has been validated theoretically and experimentally. [20] Nevertheless, it still suffers from high overpotential and competitive HER, which could be optimized by further modification such as transition metal (oxide) deposition.…”

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confidence: 99%

Electrocatalytic Disproportionation of Nitric Oxide Toward Efficient Nitrogen Fixation

Xuan

et al. 2023

Advanced Energy Materials

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conditions (≈750 K, 150-350 atm) and fossil fuel-derived H 2 , HBP consumes approximately 2% of the world's annual energy supply and releases superabundant CO 2 . [3][4][5][6] As an appealing alternative, the electrochemical nitrogen reduction reaction (ENRR) driven by renewable energy in an aqueous environment can realize a carbon-neutral and onsite generation of NH 3 under mild conditions. [7][8][9] Nevertheless, the commercial implementation of ENRR was impeded by low NH 3 production rate and faradaic efficiency (FE), due to the high stability of the N 2 bond (NN, 948 kJ mol −1 ) and the competing hydrogen evolution reaction (HER). [10,11] Benefits from lower dissociation energy of N=O bond (204 kJ mol −1 ) and better reaction kinetics, transforming reactive nitrogen oxide into NH 3 provide a promising technical route to address the dilemma of ENRR. [12][13][14] As nitric oxide (NO) is one of the major nitrogeneous pollutants abundant in fossil fuel combustion and other chemical industry, [15,16] the rational utilization of waste NO via electrocatalysis can simultaneously alleviate the environmental load and reverse the anthropogenically Electrocatalytic conversion of waste nitric oxide into ammonia is a promising approach to achieve sustainable nitrogen fixation. Herein, a CoNi co-oxides catalyst is designed for NH 3 electrosynthesis with the merits of facilitating NO adsorption and reducing the reaction energy barrier. By synergistic coupling with anodic NO oxidation, electrocatalytic disproportionation of NO is first realized to simultaneously synthesize value-added double nitrogen products (NH 3 and nitrate) with increased total energy efficiency. Furthermore, decoupled acid-base asymmetric electrolyte design is proposed in a united assembled electrolyzer, enabling a high NH 3 production rate (26.27 mg h −1 cm −2 ) with unit faradaic efficiency and a remarkable nitrate production rate of 68.41 mg h −1 cm −2 at the anode. A low cell voltage of 3.58 V is obtained by optimizing ion agglomeration within the membrane to promote the chargeion exchange and electrode kinetics. Technoeconomic analysis demonstrates the economic feasibility of recycling waste NO by the electrocatalytic disproportionation strategy.

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“…Transitional metals (Cu, Co, Ni, and Fe) have been used as catalysts for nitrate reduction. ,, However, they usually catalyze at highly negative applied potentials (such as < −0.4 V vs RHE), which is energetically inefficient for future applications. Designing heterostructures such as metal/carbon hybrids can efficiently facilitate electron transfer and endow the structures with a large number of stable electrochemical active sites. , Metal–organic frameworks (MOFs) have attracted substantial interest owing to their tailorable derived heterostructures, compositional flexibility and the ability to form porous carbon frameworks. − These merits make the synthesis of hybrids comprising alloying metals highly feasible.…”

Section: Introductionmentioning

confidence: 99%

Energy-Efficient Ammonia Synthesis from Nitrate via CoNi Alloys Incorporated in Carbon Frameworks

Lei,

Zhang,

et al. 2023

ACS Sustainable Chem. Eng.

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As a nitrogen-containing source, nitrate is regarded as a promising precursor for generating ammonia (NH3) through electrochemical processes that can potentially mitigate the problem of groundwater contamination and the hydrogen-carrier energy crisis. Herein, we report a cobalt zeolitic imidazolate framework (ZIF-67)-derived catalyst of CoNi alloys incorporated in N-doped carbon frameworks for nitrate electroreduction. Computational results obtained using the density functional theory give a deep insight that the structure of CoNi alloys embedded in the N-doped carbon skeleton can inhibit the production of hydrogen and facilitate the hydrogenation of *NO intermediates. The enriched active sites from the ZIF-67-derived structure and the introduction of Ni in the catalyst afford desirable electrocatalytic performance. Finally, the optimized CoNi@NC hybrid can achieve an ammonia production of 168 mmol gcat –1 h–1 and a Faradaic efficiency of ∼93% at a potential as low as −0.1 V vs reversible hydrogen electrode (RHE). The highest yield rate of 1254 mmol gcat –1 h–1 can be detected at −0.6 V vs RHE. This study can inspire further development of non-noble metal-based hybrid electrocatalysts for nitrate reduction and also anticipation into sustainable synthesis of carbon-related fuels from CO2 reduction.

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Boosting Electrocatalytic Nitrate-to-Ammonia Conversion via Plasma Enhanced CuCo Alloy–Substrate Interaction

Cited by 26 publications

References 51 publications

Combined Effects of Concentration, pH, and Polycrystalline Copper Surfaces on Electrocatalytic Nitrate-to-Ammonia Activity and Selectivity

Combined Effects of Concentration, pH, and Polycrystalline Copper Surfaces on Electrocatalytic Nitrate-to-Ammonia Activity and Selectivity

Electrocatalytic Disproportionation of Nitric Oxide Toward Efficient Nitrogen Fixation

Energy-Efficient Ammonia Synthesis from Nitrate via CoNi Alloys Incorporated in Carbon Frameworks

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