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Publications (10 of 156) Show all publications
Zaar, F., Olsson, S., Emanuelsson, R., Gaiser, P., Strömme, M. & Sjödin, M. (2024). Conducting redox polymers for efficient surface immobilization of molecular porphyrin catalysts. In: RCS Poster Conference 2024.: . Paper presented at RCS Poster Conference 2024. 5-6th March 2024 online.. London
Open this publication in new window or tab >>Conducting redox polymers for efficient surface immobilization of molecular porphyrin catalysts
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2024 (English)In: RCS Poster Conference 2024., London, 2024Conference paper, Poster (with or without abstract) (Refereed)
Place, publisher, year, edition, pages
London: , 2024
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-524705 (URN)
Conference
RCS Poster Conference 2024. 5-6th March 2024 online.
Available from: 2024-03-08 Created: 2024-03-08 Last updated: 2024-03-08
Zaar, F., Emanuelsson, R., Gaiser, P., Strömme, M. & Sjödin, M. (2023). Characterization and Catalytic Prospects of Metalloporphyrin-Functionalized Conducting Polymers. Electrochimica Acta, Article ID 143003.
Open this publication in new window or tab >>Characterization and Catalytic Prospects of Metalloporphyrin-Functionalized Conducting Polymers
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2023 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, article id 143003Article in journal (Refereed) Published
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-509759 (URN)10.2139/ssrn.4494116 (DOI)
Available from: 2023-08-22 Created: 2023-08-22 Last updated: 2023-08-22
Zaar, F., Emanuelsson, R., Gaiser, P., Strömme, M. & Sjödin, M. (2023). Characterization and catalytic prospects of metalloporphyrin-functionalized conducting polymers. Electrochimica Acta, 467, Article ID 143003.
Open this publication in new window or tab >>Characterization and catalytic prospects of metalloporphyrin-functionalized conducting polymers
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2023 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 467, article id 143003Article in journal (Refereed) Published
Abstract [en]

Molecular catalysts are attracting interest as drivers of redox reactions for sustainable applications. Through systematic molecular design, they could be engineered to have high selectivity and activity towards a multitude of catalytic reactions. However, as long as they are used in homogeneous setups, they will suffer from inconvenient energy supply, inefficient charge transport and difficulty in separation from reaction products. To be relevant for industrial applications, molecular catalysts must be bound to solid materials in direct contact with the energy source. In this regard, conducting polymers are particularly interesting, as they provide a straightforward means of both surface immobilization and charge transport. In this work, we synthesize and characterize three different metalloporphyrin-functionalized conducting polymers and apply them to catalysis of the hydrogen evolution reaction (HER) and the oxygen reduction reaction (ORR). We show that incorporation of porphyrins into conducting polymers is a reliable immobilization method, that the properties of both the porphyrin units and the polymer backbone are preserved in all systems, and that the polymers provide efficient charge transport to and from the catalytic centers. Nevertheless, we also find that the polymers are negatively affected by intermediates formed during the HER and the ORR. We conclude that the choice of immobilization method has a large impact on the quality of the molecular catalyst, and that the effect of the catalytic cycle on the immobilization matrix must be considered in the molecular design process.

Place, publisher, year, edition, pages
Elsevier BV, 2023
Keywords
Conducting polymers, Porphyrins, Electrocatalysis, Redox chemistry, Reaction kinetics
National Category
Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-514756 (URN)10.1016/j.electacta.2023.143003 (DOI)001075908300001 ()
Funder
Swedish Research Council Formas, 2019-01285
Available from: 2023-10-24 Created: 2023-10-24 Last updated: 2023-10-24Bibliographically approved
Sjödin, M., Emanuelsson, R., Strietzel, C., Wang, H. & Strömme, M. (2023). Conducting Redox Polymers as Active Materials in Secondary Batteries. In: International Society of Electrochemistry (Ed.), 74th Annual Meeting of the International Society of Electrochemistry: . Paper presented at 74th Annual Meeting of the International Society of Electrochemistry 3/9 -8/9 Lyon. France.
Open this publication in new window or tab >>Conducting Redox Polymers as Active Materials in Secondary Batteries
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2023 (English)In: 74th Annual Meeting of the International Society of Electrochemistry / [ed] International Society of Electrochemistry, 2023Conference paper, Oral presentation with published abstract (Refereed)
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials; Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-509871 (URN)
Conference
74th Annual Meeting of the International Society of Electrochemistry 3/9 -8/9 Lyon. France
Available from: 2023-08-23 Created: 2023-08-23 Last updated: 2023-08-23
Sjödin, M., Rikard, E., Strietzel, C., Wang, H. & Strömme, M. (2023). Conducting Redox Polymers as Active Materials in Secondary Batteries. In: : . Paper presented at 74th Annual Meeting of the International Society of Electrochamistry.
Open this publication in new window or tab >>Conducting Redox Polymers as Active Materials in Secondary Batteries
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2023 (English)Conference paper, Oral presentation with published abstract (Refereed)
National Category
Other Materials Engineering
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-516846 (URN)
Conference
74th Annual Meeting of the International Society of Electrochamistry
Available from: 2023-11-30 Created: 2023-11-30 Last updated: 2023-11-30
Zaar, F., Araujo, M., Emanuelsson, R., Olsson, S. K., Strömme, M. & Sjödin, M. (2023). Molecular volcano plots: thermodynamically sound but kinetically insufficient. In: : . Paper presented at FEMS EUROMAT 2023.
Open this publication in new window or tab >>Molecular volcano plots: thermodynamically sound but kinetically insufficient
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2023 (English)Conference paper, Oral presentation with published abstract (Other academic)
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials; Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-510163 (URN)
Conference
FEMS EUROMAT 2023
Available from: 2023-08-24 Created: 2023-08-24 Last updated: 2023-08-24
Zaar, F., Araujo, M., Emanuelsson, R., Strömme, M. & Sjödin, M. (2023). Tetraphenylporphyrin electrocatalysts for the hydrogen evolution reaction: applicability of molecular volcano plots to experimental operating conditions. Dalton Transactions, 52(30), 10348-10362
Open this publication in new window or tab >>Tetraphenylporphyrin electrocatalysts for the hydrogen evolution reaction: applicability of molecular volcano plots to experimental operating conditions
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2023 (English)In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, Vol. 52, no 30, p. 10348-10362Article in journal (Refereed) Published
Abstract [en]

Recent years have seen an increasing interest in molecular electrocatalysts for the hydrogen evolution reaction (HER). Efficient hydrogen evolution would play an important role in a sustainable fuel economy, and molecular systems could serve as highly specific and tunable alternatives to traditional noble metal surface catalysts. However, molecular catalysts are currently mostly used in homogeneous setups, where quantitative evaluation of catalytic activity is non-standardized and cumbersome, in particular for multistep, multielectron processes. The molecular design community would therefore be well served by a straightforward model for prediction and comparison of the efficiency of molecular catalysts. Recent developments in this area include attempts at applying the Sabatier principle and the volcano plot concept – popular tools for comparing metal surface catalysts – to molecular catalysis. In this work, we evaluate the predictive power of these tools in the context of experimental operating conditions, by applying them to a series of tetraphenylporphyrins employed as molecular electrocatalysts of the HER. We show that the binding energy of H and the redox chemistry of the porphyrins depend solely on the electron withdrawing ability of the central metal ion, and that the thermodynamics of the catalytic cycle follow a simple linear free energy relation. We also find that the catalytic efficiency of the porphyrins is almost exclusively determined by reaction kinetics and therefore cannot be explained by thermodynamics alone. We conclude that the Sabatier principle, linear free energy relations and molecular volcano plots are insufficient tools for predicting and comparing activity of molecular catalysts, and that experimentally useful information of catalytic performance can still only be obtained through detailed knowledge of the catalytic pathway for each individual system.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2023
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-510161 (URN)10.1039/d3dt01250f (DOI)001030623300001 ()
Available from: 2023-08-24 Created: 2023-08-24 Last updated: 2023-10-09Bibliographically approved
Sjödin, M. (2023). Towards net-zero carbon economy in Scandinavia. In: : . Paper presented at Energy and Nanomaterials for a Carbon Neutral Society in a Sustainable Future.
Open this publication in new window or tab >>Towards net-zero carbon economy in Scandinavia
2023 (English)Conference paper, Oral presentation with published abstract (Other academic)
National Category
Climate Research
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-516849 (URN)
Conference
Energy and Nanomaterials for a Carbon Neutral Society in a Sustainable Future
Available from: 2023-11-30 Created: 2023-11-30 Last updated: 2023-11-30
Zaar, F., Olsson, S., Emanuelsson, R., Strömme, M. & Sjödin, M. (2022). Characterization of a porphyrin-functionalized conducting polymer: A first step towards sustainable electrocatalysis. Electrochimica Acta, 424, Article ID 140616.
Open this publication in new window or tab >>Characterization of a porphyrin-functionalized conducting polymer: A first step towards sustainable electrocatalysis
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2022 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 424, article id 140616Article in journal (Refereed) Published
Abstract [en]

The climate crisis has created a demand for molecular catalysts that can drive redox reactions for production of sustainable fuels. To this end, we present the design, synthesis and characterization of a conducting polymer backbone functionalized with free base porphyrin pendant groups. Combining intrinsic charge transport with catalytic prospect, this system offers possibilities of molecular heterogeneous electrocatalysis with straightforward energy supply and product extraction. Using cyclic voltammetry and spectroelectrochemistry, we show that the polymerized system is stable, and that the properties of the polymer and the porphyrins are independently preserved. With in-situ conductance measurements, we demonstrate that polaronic charge transport through the polymer backbone is superimposed by redox conductivity through the porphyrin pendant groups. These results suggest that our system is a reliable fundamental structure suitable for tuning towards heterogeneous catalysis of redox reactions.

Place, publisher, year, edition, pages
Elsevier, 2022
Keywords
Conducting polymers, Porphyrins, Electrocatalysis, Molecular design, Spectroelectrochemistry
National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-480966 (URN)10.1016/j.electacta.2022.140616 (DOI)000833422700007 ()
Funder
Swedish Energy AgencySwedish Research Council Formas
Available from: 2022-07-26 Created: 2022-07-26 Last updated: 2024-01-15Bibliographically approved
Zaar, F., Olsson, S., Emanuelsson, R., Gaiser, P., Strömme, M. & Sjödin, M. (2022). Conducting redox polymers for efficient surface immobilization of molecular porphyrin catalysts. In: : . Paper presented at The 19th International Symposium on Novel Aromatic Compounds, Warsaw, July 3-8 2022..
Open this publication in new window or tab >>Conducting redox polymers for efficient surface immobilization of molecular porphyrin catalysts
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2022 (English)Conference paper, Poster (with or without abstract) (Other academic)
Abstract [en]

Efficient molecular electrocatalysts are a vital part of the ongoing transition towards sustainable fuel production and away from expensive traditional noble metal catalysts. Molecular catalysts can be synthesized from earth-abundant elements and have well-defined catalytic sites [1], but are associated with poor electronic connection and impractical product separation in homogeneous setups [1-2].

We have synthesized and characterized a conducting redox polymer [3–4] consisting of a conjugated EDOT-based polymer functionalized with free base porphyrins. The polymer allows for simple surface immobilization, a higher number of catalytic units than a monolayer, and continuous charge transport to and from the redox centers of the porphyrins over a large potential window. The porphyrins are aromatic macrocyclic ligands with a rich redox chemistry that can be metallated with a wide variety of metals. Through substitution and metalation, the catalytic selectivity of these redox non-innocent compounds can be tuned towards environmentally beneficial redox reactions, such as solar-powered hydrogen evolution or CO2 reduction.

Through electrochemical analysis, we have established that the individual properties of the system building-blocks are preserved, that the polymer improves porphyrin reaction kinetics, that the porphyrins are efficient conduits for electron transfer, and that the porphyrin pendant units can be metallated before or after polymerization. The system should thus be regarded as a stable fundamental platform that through appropriate molecular fine-tuning can be can be used for heterogeneous catalysis of environmentally beneficial redox reactions.

References 

[1] A. Corma, H. Garcia, Top. Catal. 48 (2008) 8.

[2] W. Herrmann, C. Kohlpaintner, Angew. Chem. Int. Ed. Engl. 32 (1993) 1524.

[3] M. Sterby, R. Emanuelsson, F. Mamedov, M. Strømme, M. Sjödin, Electrochim. Acta. 308 (2019) 277.

[4] G. Zotti, A. Berlin, G. Pagani, G. Schiavon, S. Zecchin, Adv. Mater. 7 (1995) 48.

National Category
Nano Technology
Research subject
Engineering Science with specialization in Nanotechnology and Functional Materials
Identifiers
urn:nbn:se:uu:diva-489440 (URN)
Conference
The 19th International Symposium on Novel Aromatic Compounds, Warsaw, July 3-8 2022.
Available from: 2022-11-30 Created: 2022-11-30 Last updated: 2022-12-02Bibliographically approved
Organisations
Identifiers
ORCID iD: ORCID iD iconorcid.org/0000-0003-4126-4347

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