[{"language":[{"iso":"eng"}],"scopus_import":"1","publisher":"American Chemical Society","oaworkID":1,"date_published":"2024-01-08T00:00:00Z","article_type":"original","month":"01","date_created":"2024-01-17T12:48:35Z","department":[{"_id":"MaIb"}],"status":"public","intvolume":"         7","type":"journal_article","day":"08","page":"214-229","publication":"ACS Applied Energy Materials","issue":"1","external_id":{"oaworkID":["w4389780443"],"isi":["001138342900001"]},"title":"Interface engineering modulation combined with electronic structure modification of Zn-doped NiO heterostructure for efficient water-splitting activity","year":"2024","doi":"10.1021/acsaem.3c02519","isi":1,"author":[{"full_name":"Kiran, Gundegowda Kalligowdanadoddi","last_name":"Kiran","first_name":"Gundegowda Kalligowdanadoddi"},{"id":"12d625da-9cb3-11ed-9667-af09d37d3f0a","orcid":"0000-0003-2209-5269","full_name":"Singh, Saurabh","last_name":"Singh","first_name":"Saurabh"},{"full_name":"Mahato, Neelima","last_name":"Mahato","first_name":"Neelima"},{"first_name":"Thupakula Venkata Madhukar","full_name":"Sreekanth, Thupakula Venkata Madhukar","last_name":"Sreekanth"},{"full_name":"Dillip, Gowra Raghupathy","last_name":"Dillip","first_name":"Gowra Raghupathy"},{"last_name":"Yoo","full_name":"Yoo, Kisoo","first_name":"Kisoo"},{"first_name":"Jonghoon","full_name":"Kim, Jonghoon","last_name":"Kim"}],"keyword":["Electrical and Electronic Engineering","Materials Chemistry","Electrochemistry","Energy Engineering and Power Technology","Chemical Engineering (miscellaneous)"],"abstract":[{"text":"Production of hydrogen at large scale requires development of non-noble, inexpensive, and high-performing catalysts for constructing water-splitting devices. Herein, we report the synthesis of Zn-doped NiO heterostructure (ZnNiO) catalysts at room temperature via a coprecipitation method followed by drying (at 80 °C, 6 h) and calcination at an elevated temperature of 400 °C for 5 h under three distinct conditions, namely, air, N2, and vacuum. The vacuum-synthesized catalyst demonstrates a low overpotential of 88 mV at −10 mA cm–2 and a small Tafel slope of 73 mV dec–1 suggesting relatively higher charge transfer kinetics for hydrogen evolution reactions (HER) compared with the specimens synthesized under N2 or O2 atmosphere. It also demonstrates an oxygen evolution (OER) overpotential of 260 mV at 10 mA cm–2 with a low Tafel slope of 63 mV dec–1. In a full-cell water-splitting device, the vacuum-synthesized ZnNiO heterostructure demonstrates a cell voltage of 1.94 V at 50 mA cm–2 and shows remarkable stability over 24 h at a high current density of 100 mA cm–2. It is also demonstrated in this study that Zn-doping, surface, and interface engineering in transition-metal oxides play a crucial role in efficient electrocatalytic water splitting. Also, the results obtained from density functional theory (DFT + U = 0–8 eV), where U is the on-site Coulomb repulsion parameter also known as Hubbard U, based electronic structure calculations confirm that Zn doping constructively modifies the electronic structure, in both the valence band and the conduction band, and found to be suitable in tailoring the carrier’s effective masses of electrons and holes. The decrease in electron’s effective masses together with large differences between the effective masses of electrons and holes is noticed, which is found to be mainly responsible for achieving the best water-splitting performance from a 9% Zn-doped NiO sample prepared under vacuum.","lang":"eng"}],"citation":{"chicago":"Kiran, Gundegowda Kalligowdanadoddi, Saurabh Singh, Neelima Mahato, Thupakula Venkata Madhukar Sreekanth, Gowra Raghupathy Dillip, Kisoo Yoo, and Jonghoon Kim. “Interface Engineering Modulation Combined with Electronic Structure Modification of Zn-Doped NiO Heterostructure for Efficient Water-Splitting Activity.” <i>ACS Applied Energy Materials</i>. American Chemical Society, 2024. <a href=\"https://doi.org/10.1021/acsaem.3c02519\">https://doi.org/10.1021/acsaem.3c02519</a>.","ieee":"G. K. Kiran <i>et al.</i>, “Interface engineering modulation combined with electronic structure modification of Zn-doped NiO heterostructure for efficient water-splitting activity,” <i>ACS Applied Energy Materials</i>, vol. 7, no. 1. American Chemical Society, pp. 214–229, 2024.","apa":"Kiran, G. K., Singh, S., Mahato, N., Sreekanth, T. V. M., Dillip, G. R., Yoo, K., &#38; Kim, J. (2024). Interface engineering modulation combined with electronic structure modification of Zn-doped NiO heterostructure for efficient water-splitting activity. <i>ACS Applied Energy Materials</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/acsaem.3c02519\">https://doi.org/10.1021/acsaem.3c02519</a>","ista":"Kiran GK, Singh S, Mahato N, Sreekanth TVM, Dillip GR, Yoo K, Kim J. 2024. Interface engineering modulation combined with electronic structure modification of Zn-doped NiO heterostructure for efficient water-splitting activity. ACS Applied Energy Materials. 7(1), 214–229.","short":"G.K. Kiran, S. Singh, N. Mahato, T.V.M. Sreekanth, G.R. Dillip, K. Yoo, J. Kim, ACS Applied Energy Materials 7 (2024) 214–229.","ama":"Kiran GK, Singh S, Mahato N, et al. Interface engineering modulation combined with electronic structure modification of Zn-doped NiO heterostructure for efficient water-splitting activity. <i>ACS Applied Energy Materials</i>. 2024;7(1):214-229. doi:<a href=\"https://doi.org/10.1021/acsaem.3c02519\">10.1021/acsaem.3c02519</a>","mla":"Kiran, Gundegowda Kalligowdanadoddi, et al. “Interface Engineering Modulation Combined with Electronic Structure Modification of Zn-Doped NiO Heterostructure for Efficient Water-Splitting Activity.” <i>ACS Applied Energy Materials</i>, vol. 7, no. 1, American Chemical Society, 2024, pp. 214–29, doi:<a href=\"https://doi.org/10.1021/acsaem.3c02519\">10.1021/acsaem.3c02519</a>."},"publication_status":"published","quality_controlled":"1","oa_version":"None","acknowledgement":"This work was supported by the Technology Innovation Program (20011622, Development of Battery System Applied High-Efficiency Heat Control Polymer and Part Component) funded by the Ministry of Trade, Industry & Energy (MOTIE, Korea). Author acknowledge to Prof. Tsunehiro Takeuchi from Toyota Technological Institute, Nagoya, Japan for the support of computational resources.","user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","publication_identifier":{"issn":["2574-0962"]},"_id":"14828","article_processing_charge":"No","date_updated":"2025-07-22T14:07:29Z","volume":7},{"main_file_link":[{"url":"https://doi.org/10.1021/acsaem.3c02223","open_access":"1"}],"tmp":{"image":"/images/cc_by.png","legal_code_url":"https://creativecommons.org/licenses/by/4.0/legalcode","name":"Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)","short":"CC BY (4.0)"},"ddc":["540"],"ec_funded":1,"doi":"10.1021/acsaem.3c02223","year":"2023","title":"Exploring the landscape of heterocyclic quinones for redox flow batteries","article_processing_charge":"Yes (in subscription journal)","oa":1,"date_updated":"2024-01-08T09:03:01Z","project":[{"grant_number":"101034413","_id":"fc2ed2f7-9c52-11eb-aca3-c01059dda49c","name":"IST-BRIDGE: International postdoctoral program","call_identifier":"H2020"}],"quality_controlled":"1","oa_version":"Published Version","user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","publication_identifier":{"eissn":["2574-0962"]},"_id":"14733","citation":{"apa":"Jethwa, R. B., Hey, D., Kerber, R. N., Bond, A. D., Wright, D. S., &#38; Grey, C. P. (2023). Exploring the landscape of heterocyclic quinones for redox flow batteries. <i>ACS Applied Energy Materials</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/acsaem.3c02223\">https://doi.org/10.1021/acsaem.3c02223</a>","ieee":"R. B. Jethwa, D. Hey, R. N. Kerber, A. D. Bond, D. S. Wright, and C. P. Grey, “Exploring the landscape of heterocyclic quinones for redox flow batteries,” <i>ACS Applied Energy Materials</i>. American Chemical Society, 2023.","chicago":"Jethwa, Rajesh B, Dominic Hey, Rachel N. Kerber, Andrew D. Bond, Dominic S. Wright, and Clare P. Grey. “Exploring the Landscape of Heterocyclic Quinones for Redox Flow Batteries.” <i>ACS Applied Energy Materials</i>. American Chemical Society, 2023. <a href=\"https://doi.org/10.1021/acsaem.3c02223\">https://doi.org/10.1021/acsaem.3c02223</a>.","ama":"Jethwa RB, Hey D, Kerber RN, Bond AD, Wright DS, Grey CP. Exploring the landscape of heterocyclic quinones for redox flow batteries. <i>ACS Applied Energy Materials</i>. 2023. doi:<a href=\"https://doi.org/10.1021/acsaem.3c02223\">10.1021/acsaem.3c02223</a>","mla":"Jethwa, Rajesh B., et al. “Exploring the Landscape of Heterocyclic Quinones for Redox Flow Batteries.” <i>ACS Applied Energy Materials</i>, American Chemical Society, 2023, doi:<a href=\"https://doi.org/10.1021/acsaem.3c02223\">10.1021/acsaem.3c02223</a>.","ista":"Jethwa RB, Hey D, Kerber RN, Bond AD, Wright DS, Grey CP. 2023. Exploring the landscape of heterocyclic quinones for redox flow batteries. ACS Applied Energy Materials.","short":"R.B. Jethwa, D. Hey, R.N. Kerber, A.D. Bond, D.S. Wright, C.P. Grey, ACS Applied Energy Materials (2023)."},"publication_status":"epub_ahead","author":[{"first_name":"Rajesh B","full_name":"Jethwa, Rajesh B","last_name":"Jethwa","orcid":"0000-0002-0404-4356","id":"4cc538d5-803f-11ed-ab7e-8139573aad8f"},{"first_name":"Dominic","full_name":"Hey, Dominic","last_name":"Hey"},{"last_name":"Kerber","full_name":"Kerber, Rachel N.","first_name":"Rachel N."},{"full_name":"Bond, Andrew D.","last_name":"Bond","first_name":"Andrew D."},{"first_name":"Dominic S.","last_name":"Wright","full_name":"Wright, Dominic S."},{"full_name":"Grey, Clare P.","last_name":"Grey","first_name":"Clare P."}],"keyword":["Electrical and Electronic Engineering","Materials Chemistry","Electrochemistry","Energy Engineering and Power Technology","Chemical Engineering (miscellaneous)"],"abstract":[{"text":"Redox flow batteries (RFBs) rely on the development of cheap, highly soluble, and high-energy-density electrolytes. Several candidate quinones have already been investigated in the literature as two-electron anolytes or catholytes, benefiting from fast kinetics, high tunability, and low cost. Here, an investigation of nitrogen-rich fused heteroaromatic quinones was carried out to explore avenues for electrolyte development. These quinones were synthesized and screened by using electrochemical techniques. The most promising candidate, 4,8-dioxo-4,8-dihydrobenzo[1,2-d:4,5-d′]bis([1,2,3]triazole)-1,5-diide (−0.68 V(SHE)), was tested in both an asymmetric and symmetric full-cell setup resulting in capacity fade rates of 0.35% per cycle and 0.0124% per cycle, respectively. In situ ultraviolet-visible spectroscopy (UV–Vis), nuclear magnetic resonance (NMR), and electron paramagnetic resonance (EPR) spectroscopies were used to investigate the electrochemical stability of the charged species during operation. UV–Vis spectroscopy, supported by density functional theory (DFT) modeling, reaffirmed that the two-step charging mechanism observed during battery operation consisted of two, single-electron transfers. The radical concentration during battery operation and the degree of delocalization of the unpaired electron were quantified with NMR and EPR spectroscopy.","lang":"eng"}],"department":[{"_id":"StFr"}],"has_accepted_license":"1","date_created":"2024-01-05T09:20:48Z","date_published":"2023-12-28T00:00:00Z","article_type":"original","month":"12","language":[{"iso":"eng"}],"publisher":"American Chemical Society","publication":"ACS Applied Energy Materials","type":"journal_article","day":"28","status":"public"},{"citation":{"chicago":"Kovačič, Sebastijan, Bettina Schafzahl, Nadejda B. Matsko, Katharina Gruber, Martin Schmuck, Stefan Koller, Stefan Alexander Freunberger, and Christian Slugovc. “Carbon Foams via Ring-Opening Metathesis Polymerization of Emulsion Templates: A Facile Method to Make Carbon Current Collectors for Battery Applications.” <i>ACS Applied Energy Materials</i>. American Chemical Society, 2022. <a href=\"https://doi.org/10.1021/acsaem.2c02787\">https://doi.org/10.1021/acsaem.2c02787</a>.","apa":"Kovačič, S., Schafzahl, B., Matsko, N. B., Gruber, K., Schmuck, M., Koller, S., … Slugovc, C. (2022). Carbon foams via ring-opening metathesis polymerization of emulsion templates: A facile method to make carbon current collectors for battery applications. <i>ACS Applied Energy Materials</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/acsaem.2c02787\">https://doi.org/10.1021/acsaem.2c02787</a>","ieee":"S. Kovačič <i>et al.</i>, “Carbon foams via ring-opening metathesis polymerization of emulsion templates: A facile method to make carbon current collectors for battery applications,” <i>ACS Applied Energy Materials</i>, vol. 5, no. 11. American Chemical Society, pp. 14381–14390, 2022.","short":"S. Kovačič, B. Schafzahl, N.B. Matsko, K. Gruber, M. Schmuck, S. Koller, S.A. Freunberger, C. Slugovc, ACS Applied Energy Materials 5 (2022) 14381–14390.","ista":"Kovačič S, Schafzahl B, Matsko NB, Gruber K, Schmuck M, Koller S, Freunberger SA, Slugovc C. 2022. Carbon foams via ring-opening metathesis polymerization of emulsion templates: A facile method to make carbon current collectors for battery applications. ACS Applied Energy Materials. 5(11), 14381–14390.","mla":"Kovačič, Sebastijan, et al. “Carbon Foams via Ring-Opening Metathesis Polymerization of Emulsion Templates: A Facile Method to Make Carbon Current Collectors for Battery Applications.” <i>ACS Applied Energy Materials</i>, vol. 5, no. 11, American Chemical Society, 2022, pp. 14381–90, doi:<a href=\"https://doi.org/10.1021/acsaem.2c02787\">10.1021/acsaem.2c02787</a>.","ama":"Kovačič S, Schafzahl B, Matsko NB, et al. Carbon foams via ring-opening metathesis polymerization of emulsion templates: A facile method to make carbon current collectors for battery applications. <i>ACS Applied Energy Materials</i>. 2022;5(11):14381-14390. doi:<a href=\"https://doi.org/10.1021/acsaem.2c02787\">10.1021/acsaem.2c02787</a>"},"publication_status":"published","author":[{"last_name":"Kovačič","full_name":"Kovačič, Sebastijan","first_name":"Sebastijan"},{"last_name":"Schafzahl","full_name":"Schafzahl, Bettina","first_name":"Bettina"},{"last_name":"Matsko","full_name":"Matsko, Nadejda B.","first_name":"Nadejda B."},{"last_name":"Gruber","full_name":"Gruber, Katharina","first_name":"Katharina"},{"first_name":"Martin","last_name":"Schmuck","full_name":"Schmuck, Martin"},{"first_name":"Stefan","full_name":"Koller, Stefan","last_name":"Koller"},{"id":"A8CA28E6-CE23-11E9-AD2D-EC27E6697425","first_name":"Stefan Alexander","full_name":"Freunberger, Stefan Alexander","last_name":"Freunberger","orcid":"0000-0003-2902-5319"},{"last_name":"Slugovc","full_name":"Slugovc, Christian","first_name":"Christian"}],"keyword":["Electrical and Electronic Engineering","Materials Chemistry","Electrochemistry","Energy Engineering and Power Technology","Chemical Engineering (miscellaneous)"],"abstract":[{"lang":"eng","text":"Polydicyclopentadiene (pDCPD), a thermoset with excellent mechanical properties, has enormous potential as a lightweight, tough, and stable matrix material owing to its highly cross-linked macromolecular network. This work describes generating pDCPD-based foams and hierarchically porous carbons derived therefrom by combining ring-opening metathesis polymerization (ROMP) of DCPD, high internal phase emulsions (HIPEs) as structural templates, and subsequent carbonization. The structure and function of the carbon foams were characterized and discussed in detail using scanning electron, transmission electron, or atomic force microscopy (SEM, TEM, AFM), electron energy-loss spectroscopy (TEM-EELS), N2 sorption, and analyses of electrical conductivity as well as mechanical properties. The resulting materials exhibited uniform, shape-retaining shrinkage of only ∼1/3 after carbonization. No structural failure was observed even when the pDCPD precursor foams were heated to 1400 °C. Instead, the high porosity, void size, and 3D interconnectivity were fully preserved, and the void diameters could be adjusted between 87 and 2.5 μm. Moreover, foams have a carbon content >97%, an electronic conductivity of up to 2800 S·m–1, a Young’s modulus of up to 2.1 GPa, and a specific surface area of up to 1200 m2·g–1. Surprisingly, the pDCPD foams were carbonized into shapes other than monoliths, such as 10’s of micron thick membranes or foamy coatings adhered to a metal foil or grid substrate. The latter coatings even adhere upon bending. Finally, as a use case, carbonized foams were applied as porous cathodes for Li–O2 batteries where the foams show a favorable combination of porosity, active surface area, and pore size for outstanding capacity."}],"article_processing_charge":"No","volume":5,"oa":1,"date_updated":"2023-08-04T09:27:32Z","quality_controlled":"1","oa_version":"Published Version","acknowledgement":"S.K. acknowledges the financial support from the Slovenian Research Agency (grants P1-0021, P2-0150). Support by Graz University of Technology (LP-03 – Porous Materials@Work) and from VARTA Innovation GmbH is kindly acknowledged. We thank Umicore for providing the initiator and Matjaž Mazaj (National Institute of Chemistry, Ljubljana) and Karel Jerabek (Czech Academy of Sciences) for measurements and fruitful discussions. S.A.F. is indebted to the Austrian Federal Ministry of Science, Research and Economy; the Austrian Research Promotion Agency (Grant No. 845364); and ISTA for support.","user_id":"4359f0d1-fa6c-11eb-b949-802e58b17ae8","publication_identifier":{"issn":["2574-0962"]},"_id":"12227","year":"2022","doi":"10.1021/acsaem.2c02787","title":"Carbon foams via ring-opening metathesis polymerization of emulsion templates: A facile method to make carbon current collectors for battery applications","external_id":{"isi":["000875635900001"]},"isi":1,"tmp":{"image":"/images/cc_by.png","legal_code_url":"https://creativecommons.org/licenses/by/4.0/legalcode","name":"Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)","short":"CC BY (4.0)"},"ddc":["540"],"type":"journal_article","day":"16","status":"public","intvolume":"         5","file_date_updated":"2023-01-27T09:09:15Z","page":"14381-14390","publication":"ACS Applied Energy Materials","issue":"11","date_published":"2022-10-16T00:00:00Z","article_type":"original","month":"10","language":[{"iso":"eng"}],"scopus_import":"1","publisher":"American Chemical Society","department":[{"_id":"StFr"}],"has_accepted_license":"1","file":[{"date_updated":"2023-01-27T09:09:15Z","access_level":"open_access","date_created":"2023-01-27T09:09:15Z","checksum":"572d15c250ab83d44f4e2c3aeb5f7388","file_name":"2022_AppliedEnergyMaterials_Kovacic.pdf","file_size":13105589,"file_id":"12420","creator":"dernst","content_type":"application/pdf","relation":"main_file","success":1}],"date_created":"2023-01-16T09:48:53Z"}]