Transition Metal Single‐Atom Catalysts for the Electrocatalytic Nitrate Reduction: Mechanism, Synthesis, Characterization, Application, and Prospects DOI

Tianyi Xiang,

Yuntao Liang,

Yuxi Zeng

et al.

Small, Journal Year: 2023, Volume and Issue: 19(41)

Published: June 9, 2023

Excessive accumulation of nitrate in the environment will affect human health. To combat pollution, chemical, biological, and physical technologies have been developed recently. The researcher favors electrocatalytic reduction reaction (NO3 RR) because low post-treatment cost simple treatment conditions. Single-atom catalysts (SACs) offer great activity, exceptional selectivity, enhanced stability field NO3 RR their high atomic usage distinctive structural characteristics. Recently, efficient transition metal-based SACs (TM-SACs) emerged as promising candidates for RR. However, real active sites TM-SACs applied to key factors controlling catalytic performance process remain ambiguous. Further understanding mechanism is practical significance exploring design stable SACs. In this review, from experimental theoretical studies, mechanism, rate-determining steps, essential variables affecting activity selectivity are examined. terms RR, characterization, synthesis then discussed. order promote comprehend on TM-SACs, finally highlighted, together with current problems, remedies, way forward.

Language: Английский

Electrochemical Nitrate Reduction: Ammonia Synthesis and the Beyond DOI
Yuecheng Xiong, Yunhao Wang, Jingwen Zhou

et al.

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(17)

Published: June 9, 2023

Natural nitrogen cycle has been severely disrupted by anthropogenic activities. The overuse of N-containing fertilizers induces the increase nitrate level in surface and ground waters, substantial emission oxides causes heavy air pollution. Nitrogen gas, as main component air, used for mass ammonia production over a century, providing enough nutrition agriculture to support world population increase. In last decade, researchers have made great efforts develop processes under ambient conditions combat intensive energy consumption high carbon associated with Haber-Bosch process. Among different techniques, electrochemical reduction reaction (NO

Language: Английский

Citations

239
Unveiling Cutting‐Edge Developments in Electrocatalytic Nitrate‐to‐Ammonia Conversion DOI
Haoran Zhang, Haijian Wang, X. P. Cao

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(16)

Published: Jan. 11, 2024

The excessive enrichment of nitrate in the environment can be converted into ammonia (NH

Language: Английский

Citations

175
Breaking Local Charge Symmetry of Iron Single Atoms for Efficient Electrocatalytic Nitrate Reduction to Ammonia DOI
Jingwen Xu,

Shengbo Zhang,

Hengjie Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(39)

Published: July 22, 2023

The electrochemical conversion of nitrate pollutants into value-added ammonia is a feasible way to achieve artificial nitrogen cycle. However, the development electrocatalytic nitrate-to-ammonia reduction reaction (NO3- RR) has been hampered by high overpotential and low Faradaic efficiency. Here we develop an iron single-atom catalyst coordinated with phosphorus on hollow carbon polyhedron (denoted as Fe-N/P-C) NO3- RR electrocatalyst. Owing tuning effect atoms breaking local charge symmetry single-Fe-atom catalyst, it facilitates adsorption ions enrichment some key intermediates during process. Fe-N/P-C exhibits 90.3 % efficiency yield rate 17980 μg h-1 mgcat-1 , greatly outperforming reported Fe-based catalysts. Furthermore, operando SR-FTIR spectroscopy measurements reveal pathway based observed under different applied potentials durations. Density functional theory calculations demonstrate that optimized free energy ascribed asymmetric atomic interface configuration, which achieves optimal electron density distribution. This work demonstrates critical role atomic-level precision modulation heteroatom doping for RR, providing effective strategy improving catalytic performance single atom catalysts in reactions.

Language: Английский

Citations

170
Recent Advances in Electrocatalysts for Efficient Nitrate Reduction to Ammonia DOI
Di Liu, Lulu Qiao,

Shuyang Peng

et al.

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(43)

Published: June 25, 2023

Abstract Ammonia as an irreplaceable chemical has been widely demanded to keep the sustainable development of modern society. However, its industrial production consumes huge energy and releases extraordinary green‐house gases, leading various environmental issues. To achieve green ammonia is a great challenge that extensively pursued recently. In review, most promising strategy, electrochemical nitrate reduction reaction (e‐NO 3 RR) for purpose comprehensively investigated give full understanding mechanism provide guidance future directions. Particularly, electrocatalysts focused realize high yield rate Faraday efficiency applications. The recent‐developed catalysts, including noble metallic materials, alloys, metal compounds, single‐metal‐atom metal‐free are systematically discussed review effects factors on catalytic performance in e‐NO RR. Accordingly, strategies, defects engineering, coordination environment modulating, surface controlling, hybridization, carefully improve performance, such intrinsic activity selectivity. Finally, perspectives challenges given out. This shall insightful advanced systems efficiently industry.

Language: Английский

Citations

159
Recent progress and strategies on the design of catalysts for electrochemical ammonia synthesis from nitrate reduction DOI
Wei Song,

Luchao Yue,

Xiaoya Fan

et al.

Inorganic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(12), P. 3489 - 3514

Published: Jan. 1, 2023

Ammonia (NH3) is an essential raw material in the production of fertilizers and a promising carbon-free energy carrier, however, its synthesis still depends on energy- capital-intensive Haber–Bosch process. Recently, electrochemical N2 reduction reaction has attracted significant interest as emerging method for NH3 under ambient conditions. However, limited solubility aqueous electrolyte strong NN bonds result low yield rate, inferior faradaic efficiency unsatisfactory selectivity, impeding further practical application. Considering high water nitrate (NO3−), NO3− (NO3−RR) become fascinating route achieving sustainable NH3, enormous progress been made this field. As consequence, review discusses mechanism systematically summarizes recent development electrocatalysts NO3−RR, including noble-metal-based materials, single-atom metal catalysts, transition-metal-based catalysts. Diverse design strategies catalysts to boost NO3−RR performance, such defect engineering, rational structure design, strain engineering constructing heterostructures, are discussed. This followed by illustration how robust understanding optimization affords fundamental insights into efficiency, selectivity electrocatalysts. Finally, we conclude with future perspectives critical issues, challenges research directions high-efficiency selective NH3.

Language: Английский

Citations

126
Elucidating electrochemical nitrate and nitrite reduction over atomically-dispersed transition metal sites DOI Creative Commons
Eamonn Murphy, Yuanchao Liu,

Ivana Matanović

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: July 28, 2023

Electrocatalytic reduction of waste nitrates (NO3-) enables the synthesis ammonia (NH3) in a carbon neutral and decentralized manner. Atomically dispersed metal-nitrogen-carbon (M-N-C) catalysts demonstrate high catalytic activity uniquely favor mono-nitrogen products. However, reaction fundamentals remain largely underexplored. Herein, we report set 14; 3d-, 4d-, 5d- f-block M-N-C catalysts. The selectivity NO3- to NH3 media, with specific focus on deciphering role NO2- intermediate cascade, reveals strong correlations (R=0.9) between for NH3. Moreover, theoretical computations reveal associative/dissociative adsorption pathways evolution, over normal M-N4 sites their oxo-form (O-M-N4) oxyphilic metals. This work provides platform designing multi-element NO3RR cascades single-atom or hybridization extended surfaces.

Language: Английский

Citations

122
Electro-triggered Joule heating method to synthesize single-phase CuNi nano-alloy catalyst for efficient electrocatalytic nitrate reduction toward ammonia DOI

Zunjie Zhang,

Yang Liu, Xiaozhi Su

et al.

Nano Research, Journal Year: 2023, Volume and Issue: 16(5), P. 6632 - 6641

Published: March 20, 2023

Language: Английский

Citations

86
High‐Throughput Screening of Heterogeneous Transition Metal Dual‐Atom Catalysts by Synergistic Effect for Nitrate Reduction to Ammonia DOI
Zheng Shu, Hongfei Chen, Xing Liu

et al.

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(32)

Published: May 5, 2023

Abstract Nitrate reduction to ammonia has attracted much attention for nitrate (NO 3 ‐ ) removal and (NH production. Identifying promising catalyst active electroreduction reaction RR) is critical realize efficient upscaling synthesis of NH under low‐temperature condition. For this purpose, by means spin‐polarized first‐principles calculations, the NO RR performance on a series graphitic carbon nitride (g‐CN) supported double‐atom catalysts (denoted as M 1 2 @g‐CN) are systematically investigated. The synergistic effect heterogeneous dual‐metal sites can bring out tunable activity selectivity RR. Amongst 21 candidates examined, FeMo@g‐CN CrMo@g‐CN possess high with low limiting potentials ‐0.34 ‐0.39 V, respectively. activities be attributed dimer d orbitals coupling anti‐bonding orbital . dissociation deposited FeMo CrMo dimers into two separated monomers proved difficult, ensuring kinetic stability @g‐CN. Furthermore, decorated g‐CN significantly reduces bandgap broadens adsorption window visible light, implying its great promise photocatalysis. This work opens new avenue future theoretical experimental design related photo‐/electrocatalysts.

Language: Английский

Citations

83
Crystal Phase Engineering of Ultrathin Alloy Nanostructures for Highly Efficient Electroreduction of Nitrate to Ammonia DOI Creative Commons
Yunhao Wang,

Fengkun Hao,

Mingzi Sun

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(14)

Published: Jan. 26, 2024

Abstract Electrocatalytic nitrate reduction reaction (NO 3 RR) toward ammonia synthesis is recognized as a sustainable strategy to balance the global nitrogen cycle. However, it still remains great challenge achieve highly efficient production due complex proton‐coupled electron transfer process in NO RR. Here, controlled of RuMo alloy nanoflowers (NFs) with unconventional face‐centered cubic (fcc) phase and hexagonal close‐packed/fcc heterophase for RR reported. Significantly, fcc NFs demonstrate high Faradaic efficiency 95.2% large yield rate 32.7 mg h −1 cat at 0 −0.1 V (vs reversible hydrogen electrode), respectively. In situ characterizations theoretical calculations have unraveled that possess highest d‐band center superior electroactivity, which originates from strong Ru─Mo interactions intrinsic activity phase. The optimal electronic structures supply adsorption key intermediates suppression competitive evolution, further determines remarkable performance. successful demonstration high‐performance zinc‐nitrate batteries suggests their substantial application potential electrochemical energy systems.

Language: Английский

Citations

82
Carbon‐Anchored Molybdenum Oxide Nanoclusters as Efficient Catalysts for the Electrosynthesis of Ammonia and Urea DOI

Mengmiao Sun,

Guanzheng Wu,

Jiadi Jiang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(19)

Published: March 13, 2023

Abstract The electrochemical NO 3 − reduction and its coupling with CO 2 can provide novel clean routes to synthesize NH urea, respectively. However, their practical application is still impeded by the lack of efficient catalysts desirable Faradaic efficiency (FE) yield rate. Herein, we report synthesis molybdenum oxide nanoclusters anchored on carbon black (MoO x /C) as electrocatalyst. It affords an outstanding FE 98.14 % rate 91.63 mg h −1 cat. in reduction. Besides, highest 27.7 a maximum urea 1431.5 μg toward also achieved. formation electron‐rich MoO highly unsaturated metal sites /C heterostructure beneficial for enhanced catalytic performance. Studies mechanism reveal that stabilization *NO *CO NOOH intermediates are critical synthesis,

Language: Английский

Citations

80