kth.sePublications
Change search
Link to record
Permanent link

Direct link
Brinck, Tore, ProfessorORCID iD iconorcid.org/0000-0003-2673-075X
Alternative names
Publications (10 of 145) Show all publications
Wang, J. J., Bui, T. D., Wang, X., Lv, Z., Hu, H., Kong, S., . . . Huang, F. (2025). A Copper-Zinc Cyanamide Solid-Solution Catalyst with Tailored Surface Electrostatic Potentials Promotes Asymmetric N-Intermediate Adsorption in Nitrite Electroreduction. Journal of the American Chemical Society
Open this publication in new window or tab >>A Copper-Zinc Cyanamide Solid-Solution Catalyst with Tailored Surface Electrostatic Potentials Promotes Asymmetric N-Intermediate Adsorption in Nitrite Electroreduction
Show others...
2025 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126Article in journal (Refereed) Published
Abstract [en]

The electrocatalytic nitrite reduction (NO2RR) converts nitrogen-containing pollutants to high-value ammonia (NH3) under ambient conditions. However, its multiple intermediates and multielectron coupled proton transfer process lead to low activity and NH3 selectivity for the existing electrocatalysts. Herein, we synthesize a solid-solution copper-zinc cyanamide (Cu0.8Zn0.2NCN) with localized structure distortion and tailored surface electrostatic potential, allowing for the asymmetric binding of NO2-. It exhibits outstanding NO2RR performance with a Faradaic efficiency of similar to 100% and an NH3 yield of 22 mg h(-1) cm(-2), among the best for such a process. Theoretical calculations and in situ spectroscopic measurements demonstrate that Cu-Zn sites coordinated with linear polarized [NCN](2-) could transform symmetric [Cu-O-N-O-Cu] in CuNCN-NO2- to a [Cu-N-O-Zn] asymmetric configuration in Cu0.8Zn0.2NCN-NO2-, thus enhancing adsorption and bond cleavage. A paired electro-refinery with the Cu0.8Zn0.2NCN cathode reaches 2000 mA cm(-2) at 2.36 V and remains fully operational at industrial-level 400 mA cm(-2) for >140 h with a NH3 production rate of similar to 30 mg(NH3) h(-1) cm(-2). Our work opens a new avenue of tailoring surface electrostatic potentials using a solid-solution strategy for advanced electrocatalysis.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2025
National Category
Materials Chemistry
Identifiers
urn:nbn:se:kth:diva-360823 (URN)10.1021/jacs.5c00837 (DOI)001425440100001 ()39964092 (PubMedID)2-s2.0-85217912113 (Scopus ID)
Note

QC 20250303

Available from: 2025-03-03 Created: 2025-03-03 Last updated: 2025-03-03Bibliographically approved
Brinck, T., Sagan, F. & Mitoraj, M. (2025). ETS-NOCV Analysis of σ-Donation and π-Backdonation in Complexes of Boron Based Lewis Acids with N2, CO andNH3. European Journal of Inorganic Chemistry, 28(12), Article ID e202400845.
Open this publication in new window or tab >>ETS-NOCV Analysis of σ-Donation and π-Backdonation in Complexes of Boron Based Lewis Acids with N2, CO andNH3
2025 (English)In: European Journal of Inorganic Chemistry, ISSN 1434-1948, E-ISSN 1099-1948, Vol. 28, no 12, article id e202400845Article in journal (Refereed) Published
Abstract [en]

Lewis acids B(SiR3)3 and B(GeR3)3 form anomalously strong complexes with Lewis bases N2 and CO. Intramolecular B−N/C bonds are generally in the range 1.45–1.50 Å and shorter than the sum of B and N/C covalent radii. Bonding analyses have shown that the strong bonds are a consequence of a novel σ-donation and π-backdonation mechanism, where electrons are donated into an empty sp3-type orbital on B (LUMO) from the σ-orbitals of N2/CO and electrons are backdonated from the B−Si/Ge σ-bonds into the π-type orbitals of N2/CO. Here we have analyzed the complexes between Lewis acids B(SiH3)3 and B(CF3)3 and Lewis bases N2, CO and NH3 using the extended transition state – natural orbitals for chemical valence (ETS-NOCV) method. Both σ-donation and π-backdonation are present in all complexes, and deformation densities due to the two mechanisms, i. e. NOCV pair densities, are surprisingly similar in character. Energy stabilization due to π-backdonation is much larger for the complexes of B(SiH3)3 with N2 and CO, and σ-donation stabilization is also enhanced compared to the corresponding complexes of B(CF3)3. Differential electrostatic potential indicate that the enhanced stabilization of the B(SiH3)3 complexes is largely an effect of reduced charge separation due to the balance between σ-donation and π-backdonation.

Place, publisher, year, edition, pages
Wiley, 2025
Keywords
Backdonation, Bond theory, Boron, Lewis acids, Pi-interactions, Silicon
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-363112 (URN)10.1002/ejic.202400845 (DOI)001468018100001 ()2-s2.0-105003141570 (Scopus ID)
Note

QC 20250507

Available from: 2025-05-06 Created: 2025-05-06 Last updated: 2025-05-07Bibliographically approved
Wang, J., Bui, T. D., Hu, H., Kong, S., Wang, X., Zhu, H., . . . Wang, J. (2025). Industrial-current Ammonia Synthesis by Polarized Cuprous Cyanamide Coupled to Valorization of Glycerol at 4,000 mA cm<sup>−2</sup>. Advanced Materials, 37(14), Article ID 2418451.
Open this publication in new window or tab >>Industrial-current Ammonia Synthesis by Polarized Cuprous Cyanamide Coupled to Valorization of Glycerol at 4,000 mA cm<sup>−2</sup>
Show others...
2025 (English)In: Advanced Materials, ISSN 0935-9648, E-ISSN 1521-4095, Vol. 37, no 14, article id 2418451Article in journal (Refereed) Published
Abstract [en]

The electrocatalytic nitrate reduction (NO3RR) holds significance in both NH3 synthesis and nitrate contamination remediation. However, achieving industrial-scale current and high stability in membrane electrode assembly (MEA) electrolyzer remains challenging due to inherent high full-cell voltage for sluggish NO3RR and water oxidation. Here, Cu2NCN with positive surface electrostatic potential VS(r) is applied as highly efficient NO3RR electrocatalysts to achieve industrial-current and low-voltage stable NH3 production in MEA electrolyzer with coupled anodic glycerol oxidation. This paired electro-refinery (PER) system reaches 4000 mA cm−2 at 2.52 V and remains stable at industrial-level 1000 mA cm−2 for 100 h with the NH3 production rate of 97000 µgNH3 h−1 cm−2 and a Faradaic efficiency of 83%. Theoretical calculations elucidate that the asymmetric and electron-withdrawing [N−C≡N] units enhance polarization and VS(r), promoting robust and asymmetric adsorption of NO3* on Cu2NCN to facilitate O−N bond dissociation. A comprehensive techno-economic analysis demonstrates the profitability and commercial viability of this coupled system. Our work opens a new avenue and marks a significant advancement in MEA systems for industrial NH3 synthesis.

Place, publisher, year, edition, pages
Wiley, 2025
Keywords
ammonia synthesis, nitrate reduction, paired electro-refinery system, surface electrostatic potential, techno-economic analysis
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-362538 (URN)10.1002/adma.202418451 (DOI)001427003500001 ()39981855 (PubMedID)2-s2.0-85218705780 (Scopus ID)
Note

QC 20250422

Available from: 2025-04-16 Created: 2025-04-16 Last updated: 2025-04-22Bibliographically approved
Murray, J. S., Riley, K. E. & Brinck, T. (2024). A Revival of Molecular Surface Electrostatic Potential Statistical Quantities: Ionic Solids and Liquids. Crystals, 14(11), Article ID 995.
Open this publication in new window or tab >>A Revival of Molecular Surface Electrostatic Potential Statistical Quantities: Ionic Solids and Liquids
2024 (English)In: Crystals, ISSN 2073-4352, Vol. 14, no 11, article id 995Article in journal (Refereed) Published
Abstract [en]

In this paper, we focus on surface electrostatic potentials and a variety of statistically derived quantities defined in terms of the surface potentials. These have been shown earlier to be meaningful in describing features of these potentials and have been utilized to understand the interactive tendencies of molecules in condensed phases. Our current emphasis is on ionic salts and liquids instead of neutral molecules. Earlier work on ionic salts has been reviewed. Presently, our results are for a variety of singly charged cations and anions that can combine to form ionic solids or liquids. Our approach is computational, using the density functional B3PW91/6-31G(d,p) procedure for all calculations. We find consistently that the average positive and negative surface electrostatic potentials of the cations and anions decrease with the size of the ion, as has been noted earlier. A model using computed statistical quantities has allowed us to put the melting points of both ionic solids and liquids together, covering a range from 993 °C to 11 °C.

Place, publisher, year, edition, pages
Multidisciplinary Digital Publishing Institute (MDPI), 2024
Keywords
ionic liquids, ionic salts, statistical quantities, surface areas, surface electrostatic potentials, volumes
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-357181 (URN)10.3390/cryst14110995 (DOI)001364072800001 ()2-s2.0-85210244427 (Scopus ID)
Note

QC 20241209

Available from: 2024-12-04 Created: 2024-12-04 Last updated: 2024-12-09Bibliographically approved
Sahoo, S. K. & Brinck, T. (2024). Designing V Single Atom Embedded Carbon Moiety for the Electrocatalytic Nitrogen Reduction Reaction by First Principles Study. ChemPhysChem, 25(24), Article ID e202400379.
Open this publication in new window or tab >>Designing V Single Atom Embedded Carbon Moiety for the Electrocatalytic Nitrogen Reduction Reaction by First Principles Study
2024 (English)In: ChemPhysChem, ISSN 1439-4235, E-ISSN 1439-7641, Vol. 25, no 24, article id e202400379Article in journal (Refereed) Published
Abstract [en]

Development of an efficient electrocatalyst for the nitrogen reduction reaction (NRR) to serve as a sustainable alternative to the Haber-Bosch process has proven highly challenging. Single atom catalysts (SACs), which have the maximum atom utilization efficiency, are among the most promising candidates. Single atoms can be incorporated to a catalytic system by doping or substitution or by attaching a molecular coordination complex to a substrate and the different insertion modes allow the chemical environment to be varied. We have used DFT to investigate vanadium SACS for NRR activity with a focus on varying the coordination environment of the V atom. Phthalocyanine, porphyrin and graphene like coordination environments with varying N-coordination have been studied. Vanadium phthalocyanine (VphN4) is the most promising of the investigated systems. It features high selectivity relative the HER reaction and relatively strong binding of N2 relatively H, which prevents poisoning of the surface by hydrogen. VphN4 also has the lowest overpotential among the studied systems. The electrocatalytic properties of VphN4 deposited as a monolayer on the Ag (111) surface have been investigated. This system, which already has been prepared, shows promising properties for use as a catalytic electrode for the NRR reaction

Place, publisher, year, edition, pages
Wiley, 2024
Keywords
Carbon moiety, Density functional theory, Electrocatalysis, Nitrogen reduction reaction, Single atom catalyst, Vanadium
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:kth:diva-365843 (URN)10.1002/cphc.202400379 (DOI)001344951400001 ()39213135 (PubMedID)2-s2.0-85207627896 (Scopus ID)
Note

QC 20250701

Available from: 2025-07-01 Created: 2025-07-01 Last updated: 2025-07-01Bibliographically approved
Altundas, B., Marrazzo, J. P., Brinck, T., Absil, C. & Fleming, F. F. (2024). Interrupted SNAr-Alkylation Dearomatization. JACS Au, 4(3), 1118-1124
Open this publication in new window or tab >>Interrupted SNAr-Alkylation Dearomatization
Show others...
2024 (English)In: JACS Au, E-ISSN 2691-3704, Vol. 4, no 3, p. 1118-1124Article in journal (Refereed) Published
Abstract [en]

Dearomatizations provide powerful synthetic routes to rapidly assemble substituted carbocycles and heterocycles found in a plethora of bioactive molecules. Harnessing the advantages of dearomatization typically requires vigorous reagents because of the difficulty in disrupting the stable aromatic core. A relatively mild dearomatization strategy is described that employs lithiated nitriles or isocyanides in a simple S<inf>N</inf>Ar-type addition to form σ-complexes that are trapped by alkylation. The dearomatizations are diastereoselective and efficient and rapidly install two new carbon-carbon bonds, one of which is a quaternary center, as well as nitrile, isocyanide, and cyclohexadiene functionalities.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2024
Keywords
dearomatization, interrupted SNAr, lithiated nitriles, quaternary center, σ-complexes
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-367048 (URN)10.1021/jacsau.3c00813 (DOI)001166878900001 ()38559710 (PubMedID)2-s2.0-85186098621 (Scopus ID)
Note

QC 20250714

Available from: 2025-07-14 Created: 2025-07-14 Last updated: 2025-07-14Bibliographically approved
Choi, S., Liu, C., Seo, D. H., Im, S. W., Kim, R. M., Jo, J., . . . Nam, K. T. (2024). Kink-Controlled Gold Nanoparticles for Electrochemical Glucose Oxidation. Nano Letters, 24(15), 4528-4536
Open this publication in new window or tab >>Kink-Controlled Gold Nanoparticles for Electrochemical Glucose Oxidation
Show others...
2024 (English)In: Nano Letters, ISSN 1530-6984, E-ISSN 1530-6992, Vol. 24, no 15, p. 4528-4536Article in journal (Refereed) Published
Abstract [en]

Enzymes in nature efficiently catalyze chiral organic molecules by elaborately tuning the geometrical arrangement of atoms in the active site. However, enantioselective oxidation of organic molecules by heterogeneous electrocatalysts is challenging because of the difficulty in controlling the asymmetric structures of the active sites on the electrodes. Here, we show that the distribution of chiral kink atoms on high-index facets can be precisely manipulated even on single gold nanoparticles; and this enabled stereoselective oxidation of hydroxyl groups on various sugar molecules. We characterized the crystallographic orientation and the density of kink atoms and investigated their specific interactions with the glucose molecule due to the geometrical structure and surface electrostatic potential.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2024
National Category
Materials Chemistry
Identifiers
urn:nbn:se:kth:diva-364559 (URN)10.1021/acs.nanolett.4c00413 (DOI)001197286400001 ()38573311 (PubMedID)2-s2.0-85189977851 (Scopus ID)
Funder
Swedish Research Council, 2018-05973Swedish Research Council, 2022-06725Swedish Research Council, DNR 2021-05881
Note

QC 20250616

Available from: 2025-06-16 Created: 2025-06-16 Last updated: 2025-06-16Bibliographically approved
Bui, T. D. & Brinck, T. (2024). Novel multi-functional sites in boron-based bi-atom catalysts synergistically boost C–C coupling for efficient CO electroreduction towards ethanol. Journal of Materials Chemistry A, 12(46), 32191-32203
Open this publication in new window or tab >>Novel multi-functional sites in boron-based bi-atom catalysts synergistically boost C–C coupling for efficient CO electroreduction towards ethanol
2024 (English)In: Journal of Materials Chemistry A, ISSN 2050-7488, E-ISSN 2050-7496, Vol. 12, no 46, p. 32191-32203Article in journal (Refereed) Published
Abstract [en]

Multi-active sites and electron configurations of boron-based bi-atom catalysts doped in silicene monolayers optimize adsorption behavior and facilitate the C–C coupling process for enhancement of CO reduction towards ethanol..

The electrochemical CO reduction reaction (CORR) is faced by challenges in achieving high-value-added C 2 products due to inefficient C–C bond formation and low selectivity. Using first-principles calculations, we propose a framework for boron-based bi-atom doping into a silicene monolayer (B–X@Si) to improve CORR catalytic efficiency. Transition metal (TM)-free B–B@Si and TM-containing B–Cu@Si serve as efficient bi-atom catalysts (BACs) with low limiting potentials (−0.28 and −0.63 V) and low activation barriers for C–C coupling (0.54 and 0.53 eV). The CO* binding strength of active sites with co-adsorbed CO* species follows the order TM < B < B–TM. Remarkably, the interplay within the B–TM pair strengthens CO* adsorption, driven by increased TM involvement, as characterized by the upward shift of the d-band center of TM in B–TM@Si relative to Fermi level. The coupling kinetics depend on the reactivity of C(CHO*) and CO* fragments within the decoupled CHO–CO* intermediate. Intriguingly, hetero-B–TM@Si systems display a trade-off between stronger CHO* and weaker CO* binding compared to the moderate binding observed in homo-B–B@Si. Among the TMs, Cu appears the most appropriate partner with B; the moderate synergistic effect of the B–Cu pair resulting in the smallest augmented C-affinity (CHO*) is offset by the weakest CO* binding strength on Cu itself, ensuring rapid C–C coupling similar to that of B–B@Si. Our BACs offer unique multi-functional active sites due to participation of host atoms (Si*) adjacent to the bi-dopants; these Si-atoms stabilize adsorbates, facilitate the subsequent C–C coupling step, and protect the C–O bond for selective ethanol production. This study provides theoretical insights for the development of advanced BACs with novel multi-adsorbing sites and tailored charge redistribution that enhance CO-to-C 2 conversion.

Place, publisher, year, edition, pages
Royal Society of Chemistry (RSC), 2024
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-364557 (URN)10.1039/d4ta04897k (DOI)001348501600001 ()2-s2.0-85209197562 (Scopus ID)
Funder
Swedish Research Council, 2022-06725Swedish Research Council, 2021-05881Swedish Research Council, 2022-06725Swedish Research Council, 2021-05881
Note

QC 20250616

Available from: 2025-06-16 Created: 2025-06-16 Last updated: 2025-07-08Bibliographically approved
Brinck, T. & Sahoo, S. K. (2023). Anomalous π-backbonding in complexes between B(SiR3)3 and N2: catalytic activation and breaking of scaling relations. Physical Chemistry, Chemical Physics - PCCP, 25(31), 21006-21019
Open this publication in new window or tab >>Anomalous π-backbonding in complexes between B(SiR3)3 and N2: catalytic activation and breaking of scaling relations
2023 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 25, no 31, p. 21006-21019Article in journal (Refereed) Published
Abstract [en]

Chemical transformations of molecular nitrogen (N2), including the nitrogen reduction reaction (NRR), are difficult to catalyze because of the weak Lewis basicity of N2. In this study, it is shown that Lewis acids of the types B(SiR3)3 and B(GeR3)3 bind N2 and CO with anomalously short and strong B-N or B-C bonds. B(SiH3)3·N2 has a B-N bond length of 1.48 Å and a complexation enthalpy of −15.9 kcal mol−1 at the M06-2X/jun-cc-pVTZ level. The selective binding enhancement of N2 and CO is due to π-backbonding from Lewis acid to Lewis base, as demonstrated by orbital analysis and density difference plots. The π-backbonding is found to be a consequence of constructive orbital interactions between the diffuse and highly polarizable B-Si and B-Ge bond regions and the π and π* orbitals of N2. This interaction is strengthened by electron donating substituents on Si or Ge. The π-backbonding interaction is predicted to activate N2 for chemical transformation and reduction, as it decreases the electron density and increases the length of the N-N bond. The binding of N2 and CO by the B(SiR3)3 and B(GeR3)3 types of Lewis acids also has a strong σ-bonding contribution. The relatively high σ-bond strength is connected to the highly positive surface electrostatic potential [VS(r)] above the B atom in the tetragonal binding conformation, but the σ-bonding also has a significant coordinate covalent (dative) contribution. Electron withdrawing substituents increase the potential and the σ-bond strength, but favor the binding of regular Lewis acids, such as NH3 and F−, more strongly than binding of N2 and CO. Molecules of the types B(SiR3)3 and B(GeR3)3 are chemically labile and difficult to synthesize. Heterogenous catalysts with the wanted B(Si-)3 or B(Ge-)3 bonding motif may be prepared by boron doping of nanostructured silicon or germanium compounds. B-doped and hydrogenated silicene is found to have promising properties as catalyst for the electrochemical NRR.

Place, publisher, year, edition, pages
Royal Society of Chemistry (RSC), 2023
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-338512 (URN)10.1039/d3cp00248a (DOI)001037326300001 ()37519222 (PubMedID)2-s2.0-85167399147 (Scopus ID)
Note

QC 20231114

Available from: 2023-11-14 Created: 2023-11-14 Last updated: 2023-11-14Bibliographically approved
Nyberg Borrfors, A., Harding, D. J., Weissenrieder, J., Ciaralli, S., Hallock, A. & Brinck, T. (2023). Aromatic hydrocarbons as Molecular Propellants for Electric Propulsion Thrusters. Journal of Electric Propulsion, 2(1), Article ID 24.
Open this publication in new window or tab >>Aromatic hydrocarbons as Molecular Propellants for Electric Propulsion Thrusters
Show others...
2023 (English)In: Journal of Electric Propulsion, E-ISSN 2731-4596, Vol. 2, no 1, article id 24Article in journal (Refereed) Published
Abstract [en]

The aromatic hydrocarbons (AHs) fluorobenzene, naphthalene, and 1-fluoronaphthalene are introduced as promising alternatives to xenon as propellant for in-space electric propulsion (EP). These storable molecules have similar mass, lower cost, and lower ionization energies compared to xenon, as well as the critical advantage of low post-ionization fragmentation compared to other molecular propellant candidates. The ionization characteristics of AHs are compared with those of xenon and the diamondoid adamantane, previously evaluated as a molecular propellant for EP. Quantum chemical calculations and BEB theory together with 25 eV electron ionization mass spectrometry (EI-MS) measurements have been used to predict the fragmentation of the AHs and adamantane when ionized in a plasma with an electron temperature of 7 eV (a typical electron temperature in EP plasmas). A high fraction (81 − 86%) of the detected AH ions originate from intact molecules, compared to 34% for adamantane, indicating extraordinarily low fragmentation for the selected AHs. The ionization potential of the AHs is similar to that of adamantane but lower compared to xenon (8.14–9.2 eV for the AHs, 9.25 for adamantane and 12.13 eV for xenon). BEB calculations have also been used to predict total ionization cross sections. The calculated ionization cross section of the AHs is comparable to that of adamantane but 3–5 times higher than that of xenon, which together with the low ionization potential can contribute to more efficient ionization. The AHs may have the potential to perform better than xenon, despite the absence of fragmentation in xenon.

Place, publisher, year, edition, pages
Springer Nature, 2023
Keywords
Electron impact mass spectrometry, Ion fragmentation, Ion thruster, Ionization cross section, Plasma modeling, Quantum chemical modeling
National Category
Atom and Molecular Physics and Optics
Identifiers
urn:nbn:se:kth:diva-354634 (URN)10.1007/s44205-023-00059-6 (DOI)2-s2.0-85205407277 (Scopus ID)
Note

QC 20241010

Available from: 2024-10-09 Created: 2024-10-09 Last updated: 2024-10-10Bibliographically approved
Organisations
Identifiers
ORCID iD: ORCID iD iconorcid.org/0000-0003-2673-075X

Search in DiVA

Show all publications