Sustainable nitrogen activation 2023 - Book of abstracts

Faraday Discussions Sustainable nitrogen activation - Book of abstracts 27-29 March 2023 | London, UK and online

Faraday Discussions

27-29 March 2023 | London, UK and online Sustainable nitrogen activation Book of abstracts

#FDNitrogen

Introduction

Sustainable nitrogen activation Faraday Discussion is organised by the Faraday Division of the Royal Society of Chemistry This book contains abstracts of the posters presented at Sustainable nitrogen activation Faraday Discussion. All abstracts are produced directly from typescripts supplied by authors. Copyright reserved.

Oral presentations and discussions All delegates at the meeting, not just speakers, have the opportunity to make comments, ask questions, or present complementary or contradictory measurements and calculations during the discussion. If it is relevant to the topic, you may give a 5-minute presentation of your own work during the discussion. These remarks are published alongside the papers in the final volume and are fully citable. If you would like to present slides during the discussion, please let the session chair know and load them onto the computer in the break before the start of the session. Faraday Discussion volume Copies of the discussion volume will be distributed approximately 6 months after the meeting. To expedite this, it is essential that summaries of contributions to the discussion are received no later than Friday 7 April 2023 for questions and comments and Friday 21 April 2023 for responses.

Posters Posters have been numbered consecutively: P01-P52 A poster session for the online posters will take place on Friday 24 March at 14:30 GMT.

The posters will be available to view throughout the discussion by clicking on the link in the virtual lobby. During the dedicated poster session, online authors will be available to use the networking functions in the virtual lobby. Use the inbox in the top light blue bar of the virtual lobby screen to send the poster presenter a message or request a video call with them by clicking on their name in the networking section at the bottom of the screen. A poster session for the in-person posters will take place on Monday 27 March at 18:30 BST. (The UK moves from GMT to BST on Sunday 26 March) The posters will be available to view throughout the discussion during all refreshment breaks. During the dedicated poster session, authors should stand with their poster to discuss their research with other attendees.

Poster prize The Faraday Discussions poster prize will be awarded to the best student poster as judged by the committee.

Networking sessions There will be regular breaks throughout the meeting for socialising, networking and continuing discussions started during the scientific sessions. During the networking sessions, all delegates will have access to join online networking rooms and can set theses up from the virtual lobby.

Scientific Committee

Invited Speakers

Justin Hargreaves (Chair) University of Glasgow, UK Richard Catlow UCL/Cardiff University, UK

Hideo Hosono (Introductory lecture) Tokyo Institute of Technology, Japan

Douglas MacFarlane (Closing remarks lecture) Monash University, Australia

Ping Chen Dalian Institute of Chemical Physics, China

Serena de Beer MPI Mulheim, Germany

Andrew Hector University of Southampton, UK

Marta Hartzell Georgia Institute of Technology, USA

Christopher Pickett UEA, UK

Patrick Holland Yale, USA

Kylie Vincent University of Oxford, UK

John Irvine University of St Andrews, UK

Jonas Peters CalTech, USA

Lance Seefeldt Utah State University, USA

Deniz Üner Middle East Technical University, Turkey

Faraday Discussions Forum

www.rscweb.org/forums/fd/login.php In order to record the discussion at the meeting, which forms part of the final published volume, your name and e-mail address will be stored in the Faraday Forum. This information is used for the collection of questions and responses communicated during each session. After each question or comment you will receive an e-mail which contains some keywords to remind you what you asked, and your password information for the forum. The e-mail is not a full record of your question. You need to complete your question in full on the forum . The deadline for completing questions and comments is Friday 7 April 2023

The question number in the e-mail keeps you a space on the forum. Use the forum to complete, review and expand on your question or comment. Figures and attachments can be uploaded to the forum. If you want to ask a question after the meeting, please e-mail faraday@rsc.org. Once we have received all questions and comments, responses will be invited by e-mail . These must also be completed on the forum . The deadline for completing responses is Friday 21 April 2023 . Please note that when using the Forum to submit a question or reply, your name and registered e-mail address will be visible to other delegates registered for this Faraday Discussions meeting. Key points: • The e-mail is not a full record of your comment/question. • All comments and responses must be completed in full on the forum Deadlines: Questions and comments Friday 7 April 2023 Responses Friday 21 April 2023

Poster presentations

P01

The trianionic hydrazido radical (N 2 )

3‒ : a promising functionality in N 2

chemistry? Rolando Aguilar PKU, China

P03

Catalytically-boosted hydroxyapatite/ZrO 2 nanocomposites for the heterogenous fixation of dinitrogen and water into ammonium Marc Arnau Roca Universitat Politècnica de Catalunya, Spain Effect of H 2 :N 2 ratio on the Nitridation and reaction conditions on NH 3 synthesis reaction over Ni 2 Mo 3 N Mustafa Aslan University of Glasgow, UK

P04

P05

Ammonia synthesis reaction over Co 3 Mo 3 N/SiO 2 catalyst Mustafa Aslan University of Glasgow, UK

P07

SuN2rise: the ERC-StG project targeting solar driven electrochemical Nitrogen fixation for ammonia refinery Federico Bella Politecnico di Torino, Italy Facts or artifacts: pitfalls in quantifying sub-ppm levels of ammonia produced from electrochemical nitrogen reduction Suchi Biswas JNCASR, India Towards a tunable carbon-based electrode for nitrogen reduction Craig Burdis Imperial College London, UK Lithium hydride mediates hydrogenolysis of anilines to arenes Yongli Cai University of Chinese Academy Sciences, China Synthesis of nitrogen-rich binary nitrides as new catalysts for ammonia synthesis Marianna Casavola University of Southampton, UK

P08

P10

P11

P12

P13

Low-coordinate cobalt-dinitrogen complex with high-spin configuration Ting-Yi Chen Georg-August-Universität Göttingen, Germany Hidrophobic Fe-Mo electrodes as electrocatalist for nitrogen electroreduction Rodrigo del Rio Pontificia Universidad Catolica de Chile, Chile Rapid electrolyte development for ammonia synthesis through lithium chemical looping Louis Dubrulle CEA LITEN, France

P14

P15

P16

New routes to low temperature ammonia synthesis Selin Ernam Technical University of Denmark, Denmark

P17

Aqueous photovoltaic technologies to drive electrochemical nitrogen reduction Lucia Fagiolari Politecnico di Torino, Italy Chemical looping ammonia synthesis process mediated by metal imides as nitrogen carriers Sheng Feng Chinese Academy of Sciences, China

P18

P20

Aqueous electrolyte effect on the electrochemical green ammonia production

Sara Garcia Ballesteros Politecnico di Torino, Italy

P21

Stability and bonding analysis of metal-dinitrogen bond - a deeper insight Sai Manoj Gorantla Indian Institute of Technology-Madras, India Transition-metal-free barium hydride mediates dinitrogen fixation and ammonia synthesis Yeqin Guan Dalian Institute of Chemical Physics, China

P22

P23

Barium chromium nitride-hydride for ammonia synthesis catalysis Jianping Guo Dalian Institute of Chemical Physics, China Computational screening of antiperovskite nitride materials for nitrogen chemical looping Michael Higham University College London, UK Nano-engineered electrocatalyst for nitrogen reduction reaction Ka Wai Hui University of South Australia, Australia Nitrogen reduction reaction (NRR) boosting by ionic liquids on iron-modified molybdenum sulfide electrodes Mauricio Isaacs Pontificia Universidad Católica de Chile, Chile Electrodeposits of MoSx on FTO electrodes and their application in the electrochemical redution of N 2 Mauricio Isaacs Pontificia Universidad Católica de Chile, Chile Designing mixed-metal electrocatalyst systems for photoelectrochemical nitrogen activation Manpreet Kaur University of Warwick, UK Fast, in-situ , real-time detection of ammonia in continuous electrochemical nitrogen reduction Artem Khobnya Imperial College, UK Mechanism of NH 3 synthesis over hexagonal Ca 3 CrN 3 H Yoji Kobayashi King Abdullah University of Science and Technology, Saudi Arabia Towards electrochemical control over nitrogenase crystals: structure- spectroscopy-reactivity Shoba Laxmi University of Oxford, UK

P24

P25

P26

P27

P28

P29

P30

P32

P33

Different strategies in the lithium-mediated nitrogen reduction reaction into ammonia: classification of present achievements and future

possibilities Anna Mangini Politecnico di Torino, Italy

P35

Rationally designed bimetallic iron cobalt boride for electrocatalytic N 2 reduction to ammonia Vineet Mishra Indian Institute of Technology Madras, India Gas-phase synthesis of HCN via chemical looping fixation of N 2 Spencer Mizon Imperial College, UK Is there any chance for bismuth to catalyse E-NRR in Aqueous media? Noemi Pirrone Politecnico di Torino, Italy

P36

P37

P38

Probing N 2 reduction intermediaries using in situ in operando enhanced IR spectroscopy

Johannes Rietbrock Imperial College, UK

P39

Metallic MoO 2 as a highly selective catalyst for electrochemical nitrogen fixation to ammonia under ambient conditions Muhammed NK Safeer Centre for Nano and Soft Matter Sciences, India Using citrate-gel method to fabricate Ru-Fe-N catalyst for ammonia synthesis Li Shao University of Southampton, UK

P40

P42

Bismuth based coordination polymer derived composite for electrochemical nitrogen reduction reaction Deep Lata Singh Indian Institute of Technology Madras, India

P43

N 2 activation in ammonia synthesis and cracking Collin Smith University of Cambridge, UK

P44

Trace water increases Faradaic selectivity of Li mediated nitrogen reduction Matthew Spry Imperial College, UK High temperature ammonia synthesis using mono-substituted polyoxotungstates Jake Thompson University of Glasgow, UK Hydride-based heterogeneous catalysts for ammonia synthesis: a case study of oxyhydride YHO and metal hydride YH 2 Feiyang Tian Shanghai University, China Nonaqueous LiFePO 4 reference electrode: probing potentials and Li-ion activity in Li-mediated ammonia synthesis Romain Tort Imperial College, UK Dinitrogen activation at cyclopentadienyl-phosphine iron complexes of three different valences Gao-Xiang Wang Peking University, China Shielding effect of mesoporous catalysts for plasma-enhanced catalytic synthesis of ammonia under ambient conditions Yaolin Wang University of Liverpool, UK Alkali metal doping of binary and ternary molybdenum nitrides for ammonia synthesis Rachel Young University of Glasgow, UK (n‑Bu)4NBr-Promoted N 2 splitting to molybdenum nitride Dandan Zhai Fudan University, China Dinitrogen functionalization affording chromium diazenido and side-on ƞ2-hydrazido complexes Yin Zhu-Bao Peking University, China

P45

P46

P47

P48

P49

P50

P51

P52

The trianionic hydrazido radical (N 2 )

3‒ : a promising functionality in

N 2 chemistry? Rolando Aguilar, Junnian Wei and Zhenfeng Xi Peking University, China

In molecular systems, the electrophilic derivatization of transition metal-coordinated dinitrogen (TM–N 2 ) is arguably the most utilized tactic for the functionalization of nitrogen gas. The prominence of this approach is due to the inbuilt nucleophilic character of coordinated N 2 ligands which naturally incents electrophilic pairing reactions. The rare earth elements, however, are known to activate N 2 into trianionic hydrazido radical species (N 2 ) 3‒ whose reactivity profile might enclose odd electron chemistry. In this poster, we show computational studies for a N‒C bond formation step mediated by a previously reported scandium-(N 2 ) 3– complex and propose radical pairing reactions for the functionalization of coordinated N 2 . References 1. J.R. Aguilar-Calderón, J. Wei, Z. Xi.The trianionic hydrazido radical (N 2 ) 3− : a promising platform for transforming N 2 . Inorg. Chem. Front. 2023, 10.1039/D2QI02543D

P01

Catalytically-boosted hydroxyapatite/ZrO 2 nanocomposites for the heterogenous fixation of dinitrogen and water into ammonium Marc Arnau Roca 1,2 Jordi Sans, 1,2 Pau Turon 3 and Carlos Alemán 1,2,4 1 Universitat Politècnica de Catalunya, Spain, 2 Barcelona Research Center in Multiscale Science and Engineering, Spain, 3 B. Braun Surgical, Spain, 4 Institute for Bioengineering of Catalonia (IBEC), Spain Polarized porous hydroxyapatite (HAp) based catalysts decorated with zirconia (ZrO 2 ) nanoparticles were used for the nitrogen fixation and conversion into ammonium at mild conditions, resulting in a 900 % yield increase with respect to the conventional polarized hydroxyapatite values reported in the literature 1 . Hydroxyapatite is a biocompatible ceramic material capable of demonstrating catalytic active behaviour when applyed a thermal stimulated polarization (application of a DC voltage at high temperature) thus enabling it to act as a catalyst for carbon and nitrogen fixation reactions. Porous hydroxyapatite prepared through a Pluronic® hydrogel assisted route was partially-covered with zirconia nanoparticles using electrophoretic deposition (EPD). Morphological characterization of system by means of SEM microscopy allowed zirconia nanoparticles observation (size distribution center at 300 nm). Structural studies concerning the interactions hydroxyapatite-zirconia were performed using Raman Spectroscopy, XRD and XPS confirming the correct incorporation of the nanoparticles without damaging the hydroxyapatite lattice and compromising its catalytic activation during the polarization. The polarized HAp-ZrO 2 catalysts were tested for the nitrogen fixation reactions using a batch reactor under mild conditions, specifically, 6 bar of N 2 , 120 ºC temperature, UV light (254 nm) and 20mL of water. The products obtained from this heterogenous catalysis were analysed and quantified by 1 H-NMR, displaying complete selectivity towards ammonium. Moreover, the mechanism behind the reaction process was proposed by analysing the catalyst acid/basic active sites, molecules adsorption (BET) and light absorption capabilities (UV-Vis). Overall the HAp-ZrO 2 catalytic system produced approximately 1.5 mmol/g catalyst in the span of 72 h denoting a significant increase with respect to the results published in the literature, providing an example of good synergy between polarized hydroxyapatite and zirconia nanoparticles and thus a step forward towards the use of the catalytic active HAp as a green catalyst for industrial processes involving the synthesis of ammonia. References 1. Jordi Sans, Marc Arnau, Vanesa Sanz, Pau Turon, Carlos Alemán, Fine-tuning of polarized hydroxyapatite for the catalytic conversion of dinitrogen to ammonium under mild conditions, Chemical Engineering Journal , Volume 446, Part 5, 2022, 137440, ISSN 1385-8947.

P03

Effect of H 2 :N 2 ratio on the nitridation and reaction conditions on NH 3 synthesis reaction over Ni 2 Mo 3 N Mustafa Aslan and Justin Hargreaves University of Glasgow, UK Ammonia production process consumes ca. 2% of energy production of the world annually and approximately 70% of the total cost of ammonia production is directly related with the cost of production of H 2 [1,2]. It is also the source of the 3% of the anthropogenic CO 2 production 3 . Therefore, a more sustainable way for producing ammonia is needed to decrease the carbon footprint and the cost of the production process. Molybdenum nitrides are getting attraction due to their stability, atomic nitrogen transfer ability and ammonia synthesis activity 4 . In this study, the effect of H 2 :N 2 flow ratio on both pre-treatment and reaction conditions on NH 3 synthesis reaction over Ni 2 Mo 3 N will be presented. Ni 2 Mo 3 N was synthesized using Pechini method and nitrided under H 2 :N 2 flow at 700 o C. Nitridation of the catalyst from oxide phase to nitride phase were performed with two different H 2 :N 2 ratios such as 3.0 and 0.5. While a pure phase of Ni 2 Mo 3 N was obtained when H 2 :N 2 ratio was 3.0, metallic Ni and γ-Mo 2 N impurities were observed in the XRD patterns of both fresh and spent Ni 2 Mo 3 N samples when H 2 :N 2 ratio of 0.5 was used. Ammonia synthesis activity tests were also performed under flow of different H 2 :N 2 ratios of 3.0 and 0.5 at 400 o C. The ammonia synthesis rate was measured as 117 μmol NH 3 g catalyst- 1 h -1 under flow of H 2 :N 2 ratio of 0.5 at 400 o C and atmospheric pressure and slightly higher with respect to when H 2 :N 2 ratio was 3.0. According to the characterization and reaction studies, ammonia synthesis reaction can be carried out with a lower H 2 :N 2 ratio with respect to stoichiometric ratio over Ni 2 Mo 3 N catalyst which means that may decrease the role of hydrogen in cost of ammonia production. References 1. N. Saadatjou, A. Jafari and S. Sahebdelfar, Chemical Engineering Communications, 202 (2015), 420 2. www.ammoniaenergy.org/articles/the-cost-of-co2-free-ammonia/ last accessed 16.01.2023 3. S. D. Minteer, P. Christopher and S. Linic, ACS Energy Letters, 4 (2019), 163 4. D. Mckay, D. H. Gregory, J. S. J. Hargreaves, S. M. Hunter and X. Sun, Chemical Communications, 29 (2007), 3051

P04

Ammonia synthesis reaction over Co 3 Mo 3 N/SiO 2 catalyst Mustafa Aslan and Justin Hargreaves University of Glasgow, UK

Two-thirds of the ammonia produced by Haber-Bosch process, which is operated at high temperature and pressure (400 – 500 o C, 100-300 bar), all around the world 1 . Ammonia production process consumes ca. 2% of energy production of the world annually 2 . When process economics is taken into consideration, the cost of hydrogen production is responsible for approximately 70% of cost of ammonia production 3 . Therefore, a more sustainable way for producing ammonia is needed to decrease the carbon footprint and the cost of the production process. Molybdenum nitrides are getting attraction due to their stability, atomic nitrogen transfer ability and ammonia synthesis activity 4 . Nominally 10 wt% SiO 2 supported Co 3 Mo 3 N catalyst was synthesized to investigate the effect of H 2 :N 2 ratio on the ammonia synthesis rate. Co 3 Mo 3 N/SiO 2 catalysts were prepared using incipient wetness impregnation and wet impregnation methods. The XRD patterns of the samples that was prepared using two different methods showed that Co 3 Mo 3 N phase on the sample prepared using wet impregnation has sharper crystalline peaks than the sample prepared using incipient wetness impregnation method. SEM analysis of Co 3 Mo 3 N/SiO 2 sample synthesized using wet impregnation showed that Co-Mo crystallites were located on top of SiO 2 particles. Activity studies for both samples were performed under different H 2 :N 2 flow ratios at 400 o C and atmospheric pressure. It was shown that Co 3 Mo 3 N/SiO 2 synthesized using wet impregnation method showed better NH 3 synthesis activity than Co 3 Mo 3 N/SiO 2 synthesized using incipient wetness impregnation method. In addition to this, it was observed that when H 2 :N 2 ratio decreased, NH 3 synthesis rate decreased for both catalysts. The present study showed that preparation method affected the surface distribution of the Co 3 Mo 3 N phase over SiO 2 support and thus influenced the activity and stability of the catalyst. References 1. C.P. Owens, F.E.H. Katz, C.H. Carter, V.F. Oswald, F.A. Tezcan, The Journal of American Chemical Society, 138 (2016), 10124−10127 2. N. Saadatjou, A. Jafari and S. Sahebdelfar, Chemical Engineering Communications, 202 (2015), 420 3. www.ammoniaenergy.org/articles/the-cost-of-co2-free-ammonia/last accessed 16.01.2023 4. D. Mckay, D. H. Gregory, J. S. J. Hargreaves, S. M. Hunter and X. Sun, Chemical Communications, 29 (2007), 3051

P05

SuN 2 rise: the ERC-StG project targeting solar driven electrochemical nitrogen fixation for ammonia refinery Federico Bella, Anna Mangini, Noemi Pirrone, Sara Garcia Ballesteros, Lucia Fagiolari Politecnico di Torino, Italy The preservation of our planet is the most urgent issue in the world and the scientific community is pushing a lot of researchers to work on technologies for the storage/conversion of CO 2 into chemicals. However, it is easier not to produce CO 2 than setting-up plants to treat it. In this framework, the ERC-StG project SuN 2 rise proposes an alternative breakthrough based on a versatile solar- driven strategy leading to redesign industrial processes. Facing the Haber-Bosch process for ammonia production (one of the most impactful chemical processes today), we propose the electrochemical fixation of dinitrogen into ammonia, by simply using air, water and ambient conditions. The scientific aim is that of demonstrating an integrated device where a photovoltaic (PV) unit will power a regenerative electrocatalytic cell converting dinitrogen to ammonia (E-NRR). A newly proposed Li-mediated approach under mild conditions, derived from an interdisciplinary contamination between electrocatalysis and Li-batteries, will be the key towards N 2 conversion, bypassing both the competitive hydrogen reduction reaction and the complete irreproducibility of recent E-NRR approaches attributed to N-contaminations or degradation of N-based catalysts. The team will further move beyond the state-of-the-art by fabricating transparent devices, that can be integrated in greenhouses, allowing the production of ammonia and ammonium fertilizers directly in farms, bypassing the known issues related to the massive infrastructure of ammonia plants and difficulties in reaching remote communities. The proposed approach will significantly impact also the field of liquid fuels, being ammonia safer and with higher energy density than hydrogen. Achieving these goals will require multidisciplinary expertise in the field of chemical, material, process and device engineering. References 1. This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement No. 948769, project title: SuN 2 rise).

P07

Facts or artifacts: pitfalls in quantifying sub-ppm levels of ammonia produced from electrochemical nitrogen reduction Suchi Biswas 1 , Smita Biswas 1 , Arunava Saha 1 and Muthusamy Eswaramoorthy 1,2 1 JNCASR, India, 2 International Centre for Materials Science, India In the recent years, the concept of synthesizing ammonia through electrochemical nitrogen reduction (ENR) in aqueous medium, under ambient conditions has emerged as an attractive research area. 1 However, several reports claiming high ammonia production rate, were found to falsely analyze ammonia contamination present in the surrounding as their result. 2 Even ammonia obtained from reduction of nitrogen oxides-based contaminants were also claimed as ENR result. 3 In addition to it, we observed that in majority of the cases, the concentration of ammonia quantified in the electrolyte post ENR reaction lies in the sub-ppm level. Therefore, in our work we have highlighted the artifacts present in the commonly used indophenol method for determining ammonia concentration through elaborative control experiments. It is significant to choose appropriate indophenol protocol encompassing admissible level of oxidant and a complexing agent, citrate (to mitigate the effect of interfering metal ions). Additionally, the importance to set lowest limit of ammonia concentration that can be accurately quantified by indophenol method was also justified. Further, the experimental observations were summarized into a protocol which was followed to re-evaluate the performance of two well-claimed electrocatalysts for ENR reported recently in the literature. References 1. MacFarlane, D. R. et al. A roadmap to the ammonia economy. 4 , 1186-1205 (2020). 2. Chen, G. F. et al. Advances in electrocatalytic N2 reduction—strategies to tackle the selectivity challenge. 3 , 1800337 (2019). 3. Choi, J. et al. Reassessment of the catalytic activity of bismuth for aqueous nitrogen electroreduction. 5 , 382-384 (2022).

P08

Towards a tunable carbon-based electrode for nitrogen reduction Craig Burdis , Jesús Barrio, Magda Titirici, Ifan E.L. Stephens Imperial College London, UK Lithium-mediated electrochemical nitrogen reduction to produce ammonia has been brought to the forefront of sustainable nitrogen reduction recently since it has been the only method to withstand rigorous protocols (1) In recent years, vast improvements have been made towards the selectivity and efficiency of the system by altering the composition of the electrolyte (2, 3) or by utilising a gas diffusion electrode (4) . The working electrode has been scarcely researched and thus far has been a metal current collector, commonly copper (3, 5) . Here, we are developing a tuneable carbon-based electrode which will introduce high surface area allowing for improved Faradaic Efficiencies and geometric current densities. Tuning the electrodes performance to favour lithium plating and SEI formation will be managed by altering the manufacturing process of the electrodes, namely during the pyrolysis step. References 1. Andersen, S. Z.; Čolić, V.; Yang, S.; Schwalbe, J. A.; Nielander, A. C.; McEnaney, J. M.; Enemark-Rasmussen, K.; Baker, J. G.; Singh, A. R.; Rohr, B. A.; Statt, M. J.; Blair, S. J.; Mezzavilla, S.; Kibsgaard, J.; Vesborg, P. C. K.; Cargnello, M.; Bent, S. F.; Jaramillo, T. F.; Stephens, I. E. L.; Nørskov, J. K.; Chorkendorff, I., Nature, 2019 , 570 (7762), 504–508. https://doi. org/10.1038/s41586-019-1260-x. 2. Du, H.-L., Matuszek, K., Hodgetts, R., Dinh, K., Cherepanov, P., Bakker, J. M., MacFarlane, D., &; Simonov, A. N., The chemistry of proton carriers in high-performance lithium mediated ammonia electrosynthesis. Energy &; Environmental Science , 2023 . https://doi.org/10.1039/D2EE03901 3. JWesthead, O., Spry, M., Bagger, A., Shen, Z., Yadegari, H., Favero, S., Tort, R., Titirici, M., Ryan, M. P., Jervis, R., Katayama, Y., Aguadero, A., Regoutz, A., Grimaud, A., &; Stephens, I. E. L., Journal of Materials Chemistry A , 2023 , https:// doi.org/10.1039/D2TA07686 4. ALazouski, N.; Chung, M.; Williams, K.; Gala, M. L.; Manthiram, K., Catal., 2020 , 3 (5), 463–469. https://doi.org/10.1038/ s41929-020-0455-8. 5. Li, K., Shapel, S. G., Hochfilzer, D., Pedersen, J. B., Krempl, K., Andersen, S. Z., Sažinas, R., Saccoccio, M., Li, S., Chakraborty, D., Kibsgaard, J., Vesborg, P. C. K., Nørskov, J. K., &; Chorkendorff, I., ACS Energy Letters , 2022 , 7 (1), 36–41. https://doi.org/10.1021/acsenergylett.1c02104

P10

Lithium hydride mediates hydrogenolysis of anilines to arenes Yongli Cai 1 , Liu Wei 2 , Wu Anan 2 , Guo Jianping 1 , Chen Ping 1 1 University of Chinese Academy Sciences, China, 2 Xiamen University, China. Hydrides containing hydridic H‾ have shown promise in energy storage and chemical transformations. 1 For example, alkali and alkaline earth metal hydrides (denoted as AHs) have been studied as key components of hydrogen storage materials. And some AHs (e.g., LiH and BaH 2 ) have been shown to afford nitrogen activation to form imides. Based on this knowledge, a chemical looping ammonia synthesis process mediated by AHs have been constructed, in which the formation and mutual-conversion of Li-N and Li-H bonds are the key to fulfill the loop. 2 By virtue of this unique property, we recently found that AHs can also mediate the cleavage of C-N bond in anilines besides N≡N bond. Because of high C−N bond dissociation energy, the intense coordinating ability, and the inferior leaving ability of the NH 2 group, breaking C-N bond, specially the sp 2 C-N bond remains challenging. 3 Transition metals are commonly required for C-N cleavage. The development of new strategy or materials for C-N bond activation under mild conditions will not only deepen the understanding of reaction mechanism but also have the important application value. Recently, we have proposed a lithium hydride (LiH)-mediated chemical looping process for hydrogenolysis of aniline (denoted as CL-HDN), which decouples the overall HDN reaction into a set of separated steps. 4 In the step of the loop, LiH deprotonates aniline to form a lithium anilide and H 2 . The lithium anilide is then exposed to dihydrogen at elevated temperatures to produce benzene and lithium amide (LiNH 2 ) in the step. And in the step the LiH is regenerated by the hydrogenation of LiNH 2 in a flow of H 2 closing the chemical cycle. Benzene is the dominant denitrogenated product in this process. A high denitrogenated product formation rate is achieved under lower temperatures and pressures which is comparable to the catalytic rate of transition metal catalysts. The computational studies reveal that the cleavage of C-N bond is facilitated via a LiH-mediated pathway, in which the hydride (Hˉ) of LiH functions as a nucleophile to attack the α-sp 2 C atom and Li cation interacts with the distorted aromatic ring by a cation−π interaction. This work provides a new method for C-N bond activation and may help the development of new materials or catalysts for the C-N bond cleavage. Considering the reaction is an inverse step of C-N bond formation, this work also provides hints on the development of efficient materials or processes for the reaction of benzene and ammonia to anilines or other important C-X (X=C, O etc.) bond coupling reactions. References 1. Q. Wang, J. Guo*, P. Chen*, Joule , 2020 , 4, 705-709.

2. W. Gao, J. Guo*, P. Chen* et al., Nat. Energy ., 2018 , 3, 1067-1075. 3. D. Hu, Y. Zhou, X. Jiang*, Natl. Sci. Rev., 2022 , 9, No. nwab156. 4. Y. Cai, J. Guo*, P. Chen* et al., J. Am. Chem. Soc. , 2022 , 144, 17441−17448.

P11

Synthesis of nitrogen-rich binary nitrides as new catalysts for ammonia synthesis Marianna Casavola 1 , Min Zhang 1 , Angela Daisley 2 , Justin Hargreaves 2 and Andrew L. Hector 1 1 University of Southampton, UK, 2 University of Glasgow, UK Ammonia plays a key role in the transition to a carbon neutral, renewable energy production and significant efforts in the scientific community are devoted to develop new catalysts to synthesise ammonia in a cost-effective, scalable and safe way. 1 Recent studies have suggested that ammonia synthesis by nitride catalysts may occur via the Mars van Krevelen mechanism, in which intrinsic lattice nitrogen is hydrogenated, generating transient vacancies which could be replenished from the N 2 feed. The occurrence of associative reaction routes would allow to perform catalytic reactions with considerably lower energy expense compared to the most common dissociative pathways and could pave the way to a sustainable production of ammonia. 2-3 Metal nitrides with high nitrogen content, i.e. N:M ratios >1, are good candidates as catalysts for ammonia synthesis with possible looping effects. Nevertheless, transition metals usually form nitrides with lower nitrogen content, while the synthesis of higher nitrides requires more synthetic ingenuity. 4 In our group we developed wet-chemical processes at low pressure and moderate temperature to synthesise different N-rich nitrides such as Sn 3 N 4 , 5-6 Hf 3 N 4 , 7 and Zr 3 N 4 . The methods, based on a solvothermal and a combined ammonolysis/pyrolysis process, respectively, allowed for the production nitrogen-rich nitride nanopowders, which were characterised by powder XRD, SEM/EDS, TGA and ammonia synthesis catalytic tests to directly correlate structure and catalytic performance. In order to improve the catalytic properties of the nitrides, we developed a method to incorporate transition metals such as Fe in the nitrides, which could promote the reactivity of feed hydrogen and improve catalyst stability. 8-9 References 1. M. El-Shafie, S. Kambara, Recent advances in ammonia synthesis technologies: Toward future zero carbon emissions , Int. J. Hydrogen Energy, ttps://doi.org/10.1016/j.ijhydene.2022.09.061. 2. C. D. Zeinalipour-Yazdi, J. S. J. Hargreaves, and C. R. A. Catlow, J Phys Chem C, 2018, 122, 6078. 3. A. Daisley, J.S.J. Hargreaves, Metal nitrides, the Mars-van Krevelen Mechanism and Heterogeneously Catalysed Ammonia

Synthesis , Catalysis Today, 2022, doi: https://doi.org/10.1016/j.cattod.2022.08.016. 4. A. Salamat, A. L. Hector, P. Kroll, P. F. McMillan, Coord. Chem. Rev., 2013, 257, 2063. 5. X. Li, A. L. Hector, J. R. Owen and S. I. U. Shah, J. Mater. Chem. A, 2016, 4, 5081.

6. S. D. S. Fitch, G. Cibin, S. P. Hepplestone, N. Garcia-Araez and A. L. Hector, Dalton Trans., 2019, 48, 16786. 7. A. Salamat, A. L. Hector, B. M. Gray, S. A. J. Kimber, P. Bouvier, and P. F. McMillan, J. Am. Chem. Soc. 2013, 135, 9503. 8. T.-N. Ye, S.-W. Park, Y. Lu, J. Li, M. Sasase, M. Kitano, and H. Hosono, J. Am. Chem. Soc. 2020, 142, 14374. 9. T.-N. Ye, .S-W. Park, Y. Lu, J. Li, J. Wu, M. Sasase, M.i Kitano, and H. Hosono, J. Am. Chem. Soc. 2021, 143, 12857.

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Low-coordinate cobalt-dinitrogen complex with high-spin configuration Ting-Yi Chen 1 , Weiying He 1,2 Serhiy Demeshko 1 , Sebastian Dechert 1 , Serena Debeer 2 and Franc Meyer 1 1 Georg-August-Universität Göttingen, Germany and 2 MPI-CEC, Germany Binding and activation of dinitrogen at metal ions is a key step in the fixation of this inert substrate into bioavailable N-containing compounds, most prominently in the industrial Haber-Bosch process and in the enzymatic NH 3 formation mediated by nitrogenase. In the latter, N 2 is reduced at low-coordinate high-spin iron ions at the central region of the oligometallic FeMo cofactor. Numerous synthetic complexes featuring coordinated N 2 have been reported with the aim of reductive N 2 functionalization, [1,2] and in this field cobalt is emerging as a particularly promising metal ion of the 3d series, after iron. However, low-coordinate high-spin cobalt/N 2 complexes remain rare. 3 In this work, we introduce a low-coordinate high-spin dicobalt/N 2 complex, {[(IAd)Co(C(TMS) 3 )] 2 (μ-N 2 )} ( 2 ), formed from the putative two-coordinate cobalt(I) complex [(IAd)Co(C(TMS) 3 )] ( 1 ) featuring a bulky N-heterocyclic carbene (NHC) ligand IAd. Strongly s-donating NHCs have recently been introduced as valuable ligands in cobalt/N 2 chemistry. 4 The structural and spectroscopic characterization of 2 as well as its N 2 binding equilibrium in solution will be discussed. Furthermore, synchrotron-based XAS Co-L 3,2 -edge and K-edge experiments accompanied by theoretical studies have been performed to understand the unusual electronic structure and nature of N 2 binding in this new system. References 1. Y. Nishibayashi, Dalton Trans. 2018, 47, 11290-11297. 2. F. Masero, M. A. Perrin, S. Dey, V. Mougel, Chem. Eur. J. 2021, 27, 3892-3928 3. K. Ding, A. W. Pierpont, W. W. Brennessel, G. Lukat-Rodgers, K. R. Rodgers, T. R. Cundari, E. Bill, P. L. Holland. J. Am. Chem. Soc. 2009, 131, 9471-9472. 4. Y. Gao, G. Li, L. Deng, J. Am. Chem. Soc. 2018, 140, 2239-2250.

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Hidrophobic Fe-Mo electrodes as electrocatalist for nitrogen Electroreduction Rodrigo del Rio 1 , Mauricio Isaacs 1 , Daniel Correa-Encalada 1,2 , Macarena Kroff 1,2 , Galo Ramirez 1 , Enrique Dalchiele 2 , Samuel Hevia 1,2 1 Pontificia Universidad Católica de Chile, Chile, 2 Instituto de Física, Uruguay Carbon dioxide, which in 2020 reached approximately 35,000 million metric tons in emissions 1 and Ammonia production by the Haber-Bosh process may part of the problem, in 2010, out of 157.3 million metric tons of NH 3 produced, there was a total of 451 million metric tons of CO 2 emissions 2 . The electrocatalytic nitrogen reduction reaction (NRR) to obtain ammonia is a promising alternative to getting this raw material with lower greenhouse gas emissions 3, 4 . For this reason, this work shows the fabrication of Fe-Mo electrodes and their application in the electrocatalytic obtention of ammonia [4, 5]. The electrodes were prepared by applying a fixed potential on a copper electrode in FeSO 4 x7H 2 O y Na 2 MoO 4 x2H 2 O aqueous solution. The electrodes were characterized by X-Ray diffraction, FESEM microscopy and after that they were covered with Zeolitic Imidazolate Framework (ZIF-71), PVDF and PTFE films by spin coating. Different electrodes were prepared by electrolysis and tested for electrocatalysis of NRR. The best activity was found for the electrode with a 1:1 Fe:Mo composition. This electrode was characterized by FESEM and a homogeneous distribution of Fe and Mo was observed (figure 1).

These electrodes were assayed as electrocatalysts to the NRR recording polarization curves on Ar and N 2 saturated atmosphere, where the electrode with a composition of 1:1 Fe-Mo, showed a greater reduction current compared with the same experiment in absence of N 2 (Figure 2). This electrode showed a current density 40 % greater at 1.0 V. In electrolysis at 1,2 V, this electrode shows a faradaic efficiency of around 10 %. This electrode was covered with different hydrophobic films, Zeolitic Imidazolate Framework (ZIF-71), PDVF, and PTFE. The hydrophobic behavior of the modified surfaces was similar as evaluated by their contact angle. The polarization curves using the modified electrodes were evaluated by comparing the current density at -1.0 V vs Ag/AgCl and PTFE showed the best electrocatalytic behavior showing the greater difference in the current in N 2 versus Ar. This difference was 2 times at -1,0 V and 4,7 times at -1,2 V, showing that this modifier increases the hydrophobicity and avoids the interference of the hydrogen reduction.

References 1. Solution, C. o. C. a. E. Global Emissions. https://www.c2es.org/content/international-emissions/. 2. Boerner, L. K. https://cen.acs.org/environment/green-chemistry/Industrial-ammonia-production-emits-CO2/97/i24 3. Hu, L., Khaniya, A., Wang, J., Chen, G., Kaden,W.E., Feng , X., ACS Catal. 2018, 8, 9312−9319. 4. Xue Zhao, Guangzhi Hu, Gao-Feng Chen, Haibo Zhang, Shusheng Zhang, Haihui Wang Adv. Mater. 2021, 33, 2007650. 5. Lu,K.,Xia, F.,Li,B.,Liu, Y.,Razak, I.,Gao, S.,Kaelin, J.,Brown, D.E.,Cheng, Y., ACS Nano 2021, 15, 16887−16895.

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Rapid electrolyte development for ammonia synthesis through lithium chemical looping Parviz Hajiyev and Louis Dubrulle CEA LITEN, France Lately electrochemical ammonia synthesis has become very active research topic. Many different electrochemical research axes are being developed such as different electrocatalyst, aqueous and non-aqueous electrolytes, and different electrolyzer concepts. Most literature focuses on faradaic efficiency optimization; however, arguably one main challenge with electrochemical ammonia synthesis is very low synthesis rate. Which in practice limits the synthesis of enough ammonia molecules to characterize and analyze with acceptable experimental precision. Among different electrochemical ammonia synthesis approaches lithium based chemical looping approach is the most interesting. Particularly thanks to its high synthesis rate in hundreds nmol/cm 2 /s range recently reported by Hoang-Long Du et al. 1 as a successful improvement on early work of Akira Tsuneto et al 2 . The main interesting observation is that this particular performance improvement is mostly achieved by the development of a better electrolyte. This approach relies on electrochemical deposition of lithium on inert metal electrode such as copper or nickel in lithium rich electrolyte of an organic aprotic solvent (usually tetrahydrofuran). Under 10-20bar range nitrogen atmosphere, sufficient concentration of solubilized N 2 molecules are activated on the deposited lithium metal surface to form lithium nitride. Finally, the ethanol present in the electrolyte as a sacrificial proton source, protonates this nitride phase forming ammonia and liberating the lithium cation back in the electrolyte. Crucially, in this system, both nitride formation and its protonation are a chemical reaction while only lithium metal deposition is an electrochemical process. Hence, by choosing to start the ammonia synthesis from a commercial lithium metal, all the complexity associated with the electrochemical lithium deposition under 10-20 bar N 2 pressure can be avoided and rapid electrolyte development can be unlocked by using a simple pressure cell. We tested several different solvents, salts, concentrations and compared the quantity of the synthesized ammonia by uv-vis and nuclear magnetic resonance spectroscopy methods. A non-volatile solvent will have several major advantages over tetrahydrofuran for commercialization of this technology. Tetraethylene glycol dimethyl ether seems to outperform the tetrahydrofuran solvent with several different salt and concentration range. Finally, we compare these conclusions with the reproduction of improved ammonia synthesis in electrochemical pressure cell. References 1. Akira Tsuneto, Akihiko Kudo and Tadayoshi Sakata, Lithium-mediated electrochemical reduction of high pressure N 2 to NH 3 , Journal of Electroanalytical Chemistry 367 (1994) 183 2. Hoang-Long Du, Manjunath Chatti, Rebecca Y. Hodgetts, Pavel V. Cherepanov, Cuong K. Nguyen, Karolina Matuszek, Douglas R. MacFarlane, Alexandr N. Simonov, Electroreduction of nitrogen with almost 100% current-to-ammonia efficiency , Nature 609 (2022) 722

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New routes to low temperature ammonia synthesis Selin Ernam , Anastasiia Karabanova, Xiufu Sun, Peter Vang Hendriksen Technical University of Denmark, Denmark

Currently, ammonia is produced by the Haber Bosch process which involves high pressures (100 - 300 bar) and high temperatures (350 - 500 o C). Catalysts used in the Haber Bosch process show adequate activity only at higher temperatures. However, the reaction is exothermic and higher temperatures shift the equilibrium towards the reactants. To counter act this shift, pressure is increased 1 . These conditions as well as production processes for hydrogen an nitrogen, favors production in large scale facilities 2 . In contrast, a catalyst active at lower temperatures would alleviate the need for higher pressures. Milder operating conditions would facilitate small scale production of ammonia, which is highly beneficial when also considering sustainable routes to the hydrogen needed for the process. This will likely be provided via water splitting by electrolysis, which open up for decentralized production units operating on intermittently available electricity. Conventional high temperature catalysts are alkali metal promoted iron or ruthenium-based catalysts. Nitrogen and hydrogen dissociation over the catalysts are primary steps where nitrogen dissociation is the rate determining step and has a high activation barrier. The inherent problem is the scaling relation that comes with this activation barrier and the bond strength of the intermediates to the surface, making low temperature activation of such catalysts challenging. Recent advances for low temperature/pressure catalysts include ternary transition metal hydrides 3 , electrides 4 and nitrides 5 . Nitrogen activation is carried out differently over these catalysts which include associative adsorption of nitrogen followed by hydrogenation, altering the mechanism so that nitrogen dissociation is no longer the rate determining step and the Mars van Krevelen mechanism where lattice nitrogen are used and replenished by the synthesis gas respectively. Different approaches to nitrogen activation and an overview of the current progress will be discussed. Ultimately, decentralized and small-scale ammonia production units working at low temperature is the objective. Ideally, these units would operate on renewable energy. Due to the intermittent nature of renewable electricity, procedures that work well with continuous ammonia production would need modification. One such issue is the collection of produced ammonia. The poster will present our ideas for novel nitride/hydride catalysts, discuss how ammonia absorbing materials such as metal halide salts can benefit ammonia synthesis and how they can be integrated to the process. References 1. V. B. Shur and S. M. Yunusov, Russ. Chem. Bull. , 1998, 47 , 765–776. 2. M. Yoshida, T. Ogawa, Y. Imamura and K. N. Ishihara, Int. J. Hydrogen Energy , 2021, 46 , 28840–28854. 3. Q. Wang, J. Pan, J. Guo, H. A. Hansen, H. Xie, L. Jiang, L. Hua, H. Li, Y. Guan, P. Wang, W. Gao, L. Liu, H. Cao, Z. Xiong, T. Vegge and P. Chen, Nat. Catal. , 2021, 4 , 959–967. 4. M. Hara, M. Kitano and H. Hosono, ACS Catal. , 2017, 7 , 2313–2324. 5. J. S. J. Hargreaves, Appl. Petrochemical Res. , 2014, 4 , 3–10.

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Aqueous photovoltaic technologies to drive electrochemical nitrogen reduction Lucia Fagiolari , Anna Mangini, Noemi Pirrone, Sara Garcia Ballesteros, Silvia Bodoardo, Carlotta Francia, Federico Bella Politecnico di Torino, Italy The electrochemical nitrogen reduction reaction (eNRR) must be driven by renewable energy in order to be fully sustainable. Among photovoltaics, third and fourth generations are emerging as complementary to traditional silicon-based cells. These technologies are based on abundant and cheap raw materials and aim to reduce the manufacturing costs of traditional photovoltaics. In particular, dye-sensitized cells (DSSCs) offer the possibility of converting also diffuse light 1 . Currently, DSSCs with record efficiencies are based on organic volatile electrolytes, that threat the stability and the safety of the devices during operation. Water has been proposed as non-toxic, safe and environmentally friendly solvents for electrolytes, but the performances of aqueous DSSCs are still unsatisfactory 2 . To further decrease solvent evaporation and leakage from the device, (quasi)solid state electrolytes must be used. The gelification of a liquid electrolyte by using a polymer able to entrap the liquid phase could be a suitable strategy to obtain a (quasi)solid state electrolyte with properties similar to the liquid counterpart. Another strategy is the swelling of a polymeric membrane in the liquid electrolyte as well. In this view, cell components must be adapted to aqueous electrolyte and the interfacial contacts must be optimized. In a recent work 3 , we added some molecular or polymeric additives to the commercial TiO 2 paste, used to fabricate photoanodes by doctor blade technique. In same case, the modification of morphology and thickness of the sensitized photoanode could ameliorate the performance of the cell by 48% and 23%, in the case of liquid and gelified electrolyte, respectively. The use of waste-derived components is a suitable way to obtain sustainable electrolytes. In another work 4 , we employed a modified lignin in the electrolyte. Lignin is an abundant material and it is produced as waste in the paper-industry, as a byproduct of the delignification of lignocellulose. Herein, we introduced some chemical transformation in the structure and swelled the membrane in the aqueous electrolyte, to obtain a stable and sustainable DSSC. The field of aqueous photovoltaic can be further developed to be coupled with eNRR. This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement No. 948769, project title: SuN 2 rise). References 1. B. O'Regan, M. Grätzel, Nature 1991 , 353, 737-740. 2. F. Bella, C. Gerbaldi, C. Barolo, M. Grätzel, Chem. Soc. Rev . 2015 , 44, 3431-3473. 3. L. Fagiolari, M. Bonomo, A. Cognetti, G. Meligrana, C. Gerbaldi, C. Barolo, F. Bella, ChemSusChem 2020 , 13, 6562-6573. 4. J. C. de Haro, E. Tatsi, L. Fagiolari, M. Bonomo, C. Barolo, S. Turri, F. bella, G. Griffini, ACS Sustainable Chem. Eng . 2021 , 9, 8550-8560.

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Chemical looping ammonia synthesis process mediated by metal imides as nitrogen carriers Feng, Sheng 1,2 , Gao, Wenbo 2 Cao, Hujun 1 Guo, Jianping 1 Chen, Ping 1,2 1 Chinese Academy of Sciences, China, 2 Dalian University of Technology, China Ammonia is not only the main raw material of nitrogen fertilizer, but also a promising energy carrier for the storage and utilization of renewable energy. The fossil fuel-based Haber-Bosch ammonia synthesis industry is an energy- consuming and high CO 2 -emission process. For the sustainable growth of human society, it is critical important to develop “green” ammonia synthesis processes driven by renewable energy. Chemical looping process ammonia synthesis (CLAS) process involves a series of individual reactions which produce ammonia in a different manner to the catalytic process. This process has advantages in avoiding competitive adsorptions and intervening in the scaling relationships. The nitrogen carriers with favorable thermodynamic and kinetic properties are critical for such a process typically under mild conditions. Recently, we developed a chemical looping ammonia synthesis process mediated by alkali or alkaline earth metal imides as nitrogen carriers. And the kinetic performances of the imides nitrogen carriers have been improved by introducing transition metals (Fe, Co, Ni, etc.) or forming multi- functional complex nitrogen carriers (MnN-imides). In addition, we are also exploring the feasibility of changing the thermodynamic properties of CLAS by introducing external fields (electric energy, etc.). These findings have opened up new possibilities for designing and developing efficient nitrogen carriers for the CLAS process, which may be helpful to improve the chemical looping ammonia synthesis processes driven by renewable energy. References 1. Gálvez, M. E.; Halmann, M.; Steinfeld, A. Ammonia Production via a Two-Step Al 2 O 3 /AlN Thermochemical Cycle. 1. Thermodynamic, Environmental, and Economic Analyses. Ind. Eng. Chem. Res. 2007, 46 (7), 2042-2046. 2. Michalsky, R.; Avram, A. M.; Peterson, B. A.; Pfromm, P. H.; Peterson, A. A. Chemical Looping of Metal Nitride Catalysts: Low-Pressure Ammonia Synthesis for Energy Storage. Chem. Sci. 2015, 6 (7), 3965-3974. 3. McEnaney, J. M.; Singh, A. R.; Schwalbe, J. A.; Kibsgaard, J.; Lin, J. C.; Cargnello, M.; Jaramillo, T. F.; Nørskov, J. K. Ammonia Synthesis from N 2 and H 2 O Using a Lithium Cycling Electrification Strategy at Atmospheric Pressure. Energy Environ. Sci. 2017, 10 (7), 1621-1630. 4. Gao, W.; Guo, J.; Wang, P.; Wang, Q.; Chang, F.; Pei, Q.; Zhang, W.; Liu, L.; Chen, P. Production of Ammonia via a Chemical Looping Process Based on Metal Imides as Nitrogen Carriers. Nat. Energy 2018, 3 (12), 1067-1075. 5. Feng, S.; Gao, W. B.; Wang, Q. R.; Guan, Y. Q.; Yan, H. X.; Wu, H.; Cao, H. J.; Guo, J. P.; Chen, P. A Multi-Functional Composite Nitrogen Carrier for Ammonia Production via a Chemical Looping Route. J. Mater. Chem. A 2021, 9 (2), 1039- 1047.

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