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Brinck, Tore, ProfessorORCID iD iconorcid.org/0000-0003-2673-075X
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Publications (10 of 136) Show all publications
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
Bui, T. D. & Brinck, T. (2023). p-block doped semi-metallic xenes as highly selective and efficient transition-metal free single atom catalysts for electrochemical CO reduction. Journal of Materials Chemistry A, 12(4), 2110-2120
Open this publication in new window or tab >>p-block doped semi-metallic xenes as highly selective and efficient transition-metal free single atom catalysts for electrochemical CO reduction
2023 (English)In: Journal of Materials Chemistry A, ISSN 2050-7488, E-ISSN 2050-7496, Vol. 12, no 4, p. 2110-2120Article in journal (Refereed) Published
Abstract [en]

The development of robust and inexpensive catalysts for the electrochemical CO reduction reaction (CORR) is key for sustainable production of valuable chemicals, yet it remains a long-standing challenge. Herein, we conduct a systematic theoretical investigation on p-block doping of semi-metallic xene monolayers to afford transition metal free catalysts for the CORR. Silicene (Si) and germanene (Ge) are suitable platforms for capturing the dopant (B/Al) to ensure high stability. Our single atom catalysts (SACs) are promising candidates for CORR due to their favorable initial CO adsorption and the selectivity of CO reduction over H2 evolution. B@Si, Al@Si, Al@Ge and B@Ge exhibit superior CORR catalytic activity with a limiting potential UL of 0.04, −0.39, −0.40, and −0.40 V, respectively. Notably, B@Si is identified as the best CORR electrocatalyst with an overpotential of less than 0.1 V. B@Si, Al@Si, Al@Ge exhibit high CORR selectivity towards CH3OH production, whereas B@Ge is predicted to form mainly CH4. The fundamental principles behind the outstanding CORR catalytic enhancement are disclosed by analyzing the structural and electronic configurations of two key intermediates, CO* and CHO*. CO* binds the dopant with moderate strength through a combination of σ-donation and π-backdonation unique for a transition metal free catalyst, whereas CHO* adsorbs strongly to the surface by the simultaneous binding to two neighboring atomic sites; consequently, the binding of the two intermediates breaks the scaling relation that limits the CORR activity of conventional catalysts. The optimal adsorption behaviors are attributed to the surface charge modulation induced by the substitutional doping. Hence, these findings may facilitate rational design of xene-based SACs for CORR and advance other catalytic applications.

Place, publisher, year, edition, pages
Royal Society of Chemistry (RSC), 2023
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-348439 (URN)10.1039/d3ta05155b (DOI)001134351600001 ()2-s2.0-85181440760 (Scopus ID)
Note

QC 20240625

Available from: 2024-06-25 Created: 2024-06-25 Last updated: 2024-06-25Bibliographically approved
Clark, T. & Brinck, T. (2022). The Conversation on Non-Covalent Interactions: an introduction. Journal of Molecular Modeling, 28(9), Article ID 272.
Open this publication in new window or tab >>The Conversation on Non-Covalent Interactions: an introduction
2022 (English)In: Journal of Molecular Modeling, ISSN 1610-2940, E-ISSN 0948-5023, Vol. 28, no 9, article id 272Article in journal, Editorial material (Other academic) Published
Place, publisher, year, edition, pages
Springer Nature, 2022
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-318231 (URN)10.1007/s00894-022-05192-x (DOI)000844776700005 ()36006514 (PubMedID)2-s2.0-85136581834 (Scopus ID)
Note

QC 20220920

Available from: 2022-09-20 Created: 2022-09-20 Last updated: 2022-09-20Bibliographically approved
Brinck, T. & Borrfors, A. N. (2022). The Importance of Electrostatics and Polarization for Noncovalent Interactions: Ionic Hydrogen Bonds vs Ionic Halogen Bonds. Journal of Molecular Modeling, 28(9), Article ID 275.
Open this publication in new window or tab >>The Importance of Electrostatics and Polarization for Noncovalent Interactions: Ionic Hydrogen Bonds vs Ionic Halogen Bonds
2022 (English)In: Journal of Molecular Modeling, ISSN 1610-2940, E-ISSN 0948-5023, Vol. 28, no 9, article id 275Article in journal (Refereed) Published
Abstract [en]

A series of 26 hydrogen-bonded complexes between Br- and halogen, oxygen and sulfur hydrogen-bond (HB) donors is investigated at the M06-2X/6-311 +G(2df,2p) level of theory. Analysis using a model in which Br- is replaced by a point charge shows that the interaction energy (Delta E-Int) of the complexes is accurately reproduced by the scaled interaction energy with the point charge (Delta E-Int(PC)). This is demonstrated by Delta E-Int = 0.86 Delta E-Int(PC) with a correlation coefficient, R-2=0.999. The only outlier is (Br-H-Br)(-), which generally is classified as a strong charge-transfer complex with covalent character rather than a HB complex. Delta E-Int(PC) can be divided rigorously into an electrostatic contribution (Delta E-ES(PC)) and a polarization contribution (Delta E-pol(PC)).Within the set of HB complexes investigated, the former varies between -7.2 and -32.7 kcal mol(-1), whereas the latter varies between -1.6 and -11.5 kcal mol(-1). Compared to our previous study of halogen-bonded (XB) complexes between Br and C-Br XB donors, the electrostatic contribution is generally stronger and the polarization contribution is generally weaker in the HB complexes. However, for both types of bonding, the variation in interaction strength can be reproduced accurately without invoking a charge-transfer term. For the Br-center dot center dot center dot HF complex, the importance of charge penetration on the variation of the interaction energy with intermolecular distance is investigated. It is shown that the repulsive character of Delta E-Int at short distances in this complex to a large extent can be attributed to charge penetration.

Place, publisher, year, edition, pages
Springer Nature, 2022
Keywords
Hydrogen bond, Halogen bond, Electrostatic potential, Charge penetration, Intermolecular interaction
National Category
Theoretical Chemistry Physical Chemistry Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-318237 (URN)10.1007/s00894-022-05189-6 (DOI)000844776700002 ()36006525 (PubMedID)2-s2.0-85137049347 (Scopus ID)
Note

QC 20220920

Available from: 2022-09-20 Created: 2022-09-20 Last updated: 2022-09-20Bibliographically approved
Tissot, H., Stenlid, J. H., Wang, C., Panahi, M., Kaya, S., Brinck, T., . . . Weissenrieder, J. (2021). Acetic acid conversion to ketene on Cu2O(100): Reaction mechanism deduced from experimental observations and theoretical computations. Journal of Catalysis, 402, 154-165
Open this publication in new window or tab >>Acetic acid conversion to ketene on Cu2O(100): Reaction mechanism deduced from experimental observations and theoretical computations
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2021 (English)In: Journal of Catalysis, ISSN 0021-9517, E-ISSN 1090-2694, Vol. 402, p. 154-165Article in journal (Refereed) Published
Abstract [en]

Ketene, a versatile reagent in production of fine and specialty chemicals, is produced from acetic acid. We investigate the synthesis of ketene from acetic acid over the (3,0;1,1) surface of Cu2O(100) through analysis of the adsorption and desorption characteristics of formic and acetic acids. The results allow us to establish a reaction mechanism for ketene formation. Observations from x-ray photoelectron spectroscopy (XPS), scanning tunneling microscopy, and temperature programmed desorption (TPD), supported by a comparison with formic acid results, suggest that acetic acid reacts with Cu2O through deprotonation to form acetate species coordinated to copper sites and hydroxylation of nearby surface oxygen sites. For formic acid the decomposition of adsorbed formate species results in desorption of CO2 and CO while, for acetic acid, high yields of ketene are observed at temperature >500 K. Modeling by density functional theory (DFT) confirms the strong interaction of acetic acid with the (3,0;1,1) surface and the spontaneous dissociation into adsorbed acetate and hydrogen atom species, the latter forming an OH-group. In an identified reaction intermediate ketene binds via all C and O atoms to Cu surface sites, in agreement with interpretations from XPS. In the vicinity of the adsorbate the surface experiences a local reorganization into a c(2 x 2) reconstruction. The total computed energy barrier for ketene formation is 1.81 eV in good agreement with the 1.74 eV obtained from TPD analysis. Our experimental observations and mechanistic DFT studies suggests that Cu2O can operate as an efficient catalyst for the green generation of ketene from acetic acid.

Place, publisher, year, edition, pages
Elsevier BV, 2021
Keywords
Heterogeneous catalysis, Acetic acid, Ketene, Scanning tunneling microscopy, X-ray photoelectron spectroscopy, Density functional theory
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:kth:diva-303893 (URN)10.1016/j.jcat.2021.08.022 (DOI)000704425100015 ()2-s2.0-85113809250 (Scopus ID)
Note

QC 20211021

Available from: 2021-10-21 Created: 2021-10-21 Last updated: 2022-06-25Bibliographically approved
Yaempongsa, D., Brinck, A. & Brinck, T. (2021). Improving the Stability of Trinitramide by Chemical Substitution: N(NF2)(3) has Higher Stability and Excellent Propulsion Performance. Propellants, explosives, pyrotechnics, 46(2), 245-252
Open this publication in new window or tab >>Improving the Stability of Trinitramide by Chemical Substitution: N(NF2)(3) has Higher Stability and Excellent Propulsion Performance
2021 (English)In: Propellants, explosives, pyrotechnics, ISSN 0721-3115, E-ISSN 1521-4087, Vol. 46, no 2, p. 245-252Article in journal (Refereed) Published
Abstract [en]

The potential for improving the stability of trinitramide (N(NO2)(3)) by chemical substitution of the NO2 group has been investigated using Kohn-Sham density functional theory [M06-2X/6-31+G(d,p)] and ab initio quantum chemistry [CBS-QB3]. Monosubstituted analogs are generally found to have a decreased N-NO2 bond dissociation enthalpy (BDE) because of increased stabilization of the N(NO2)X radical intermediate resulting from the bond cleavage. This is particularly apparent for N(NO2)(2)NH2, which has a BDE of only 54 kJ/mol. Instead it is shown that the stability of TNA can be significantly improved by substituting all three NO2 for the NF2 group. The resulting molecule, N(NF2)(3), has a N-N BDE of 138 kJ/mol, which is 17 kJ/mol higher than the N-N BDE of N(NO2)(3). In contrast to N(NO2)(3), there are no indications that the stability of N(NF2)(3) is significantly reduced in polar solvents. Condensed phase properties of N(NF2)(3) have been estimated based on surface electrostatic potential calculations, and N(NF2)(3) is estimated to be a liquid in the approximate temperature range of 170-290 K because of its nonpolar character. The performance of N(NF2)(3) in propellant formulations with fuels rich in hydrogen and/or aluminum has been investigated. N(NF2)(3) propellants are shown to outperform propellants based on standard oxidizers by up to 20 % in specific impulse and up to 100 % in density impulse. Compositions of N(NF2)(3) and HMX have significantly higher detonation performance than CL-20.

Place, publisher, year, edition, pages
Wiley, 2021
Keywords
Oxidizer, Fluorine, Difluoroamino, Propellant, High Energy Density Material
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-296165 (URN)10.1002/prep.202000305 (DOI)000611660000001 ()2-s2.0-85099936094 (Scopus ID)
Note

QC 20220510

Available from: 2021-05-31 Created: 2021-05-31 Last updated: 2022-06-25Bibliographically approved
Jorner, K., Brinck, T., Norrby, P.-O. & Buttar, D. (2021). Machine learning meets mechanistic modelling for accurate prediction of experimental activation energies. Chemical Science, 12(3), 1163-1175
Open this publication in new window or tab >>Machine learning meets mechanistic modelling for accurate prediction of experimental activation energies
2021 (English)In: Chemical Science, ISSN 2041-6520, E-ISSN 2041-6539, Vol. 12, no 3, p. 1163-1175Article in journal (Refereed) Published
Abstract [en]

Accurate prediction of chemical reactions in solution is challenging for current state-of-the-art approaches based on transition state modelling with density functional theory. Models based on machine learning have emerged as a promising alternative to address these problems, but these models currently lack the precision to give crucial information on the magnitude of barrier heights, influence of solvents and catalysts and extent of regio- and chemoselectivity. Here, we construct hybrid models which combine the traditional transition state modelling and machine learning to accurately predict reaction barriers. We train a Gaussian Process Regression model to reproduce high-quality experimental kinetic data for the nucleophilic aromatic substitution reaction and use it to predict barriers with a mean absolute error of 0.77 kcal mol(-1) for an external test set. The model was further validated on regio- and chemoselectivity prediction on patent reaction data and achieved a competitive top-1 accuracy of 86%, despite not being trained explicitly for this task. Importantly, the model gives error bars for its predictions that can be used for risk assessment by the end user. Hybrid models emerge as the preferred alternative for accurate reaction prediction in the very common low-data situation where only 100-150 rate constants are available for a reaction class. With recent advances in deep learning for quickly predicting barriers and transition state geometries from density functional theory, we envision that hybrid models will soon become a standard alternative to complement current machine learning approaches based on ground-state physical organic descriptors or structural information such as molecular graphs or fingerprints.

Place, publisher, year, edition, pages
ROYAL SOC CHEMISTRY, 2021
National Category
Control Engineering
Identifiers
urn:nbn:se:kth:diva-291964 (URN)10.1039/d0sc04896h (DOI)000615335100035 ()36299676 (PubMedID)2-s2.0-85098937101 (Scopus ID)
Note

QC 20210323

Available from: 2021-03-23 Created: 2021-03-23 Last updated: 2023-09-21Bibliographically approved
Li, G., Stenlid, J. H., Ahlquist, M. S. G. & Brinck, T. (2020). Utilizing the Surface Electrostatic Potential to Predict the Interactions of Pt and Ni Nanoparticles with Lewis Acids and Bases-sigma-Lumps and sigma-Holes Govern the Catalytic Activities. The Journal of Physical Chemistry C, 124(27), 14696-14705
Open this publication in new window or tab >>Utilizing the Surface Electrostatic Potential to Predict the Interactions of Pt and Ni Nanoparticles with Lewis Acids and Bases-sigma-Lumps and sigma-Holes Govern the Catalytic Activities
2020 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 124, no 27, p. 14696-14705Article in journal (Refereed) Published
Abstract [en]

An improved understanding of the interactions of transition-metal (TM) nanoparticles with Lewis acids/bases will facilitate the design of more efficient catalysts. Therefore, Pt-14, Pt-13, Pt-12, and Ni-12 nanoparticles have been studied at the TPSSh/Def2-TZVP level of density functional theory (DFT). Surface electrostatic potential [V-S(r)] maps are used to analyze the Lewis acidic and basic properties of all nanoparticles and indicate that the interactions of Pt and Ni nanoparticles are governed by sigma(d)-holes and sigma(s) -holes, respectively. Lewis acids (Na+, HF) and a Lewis base (H2O) have been tested as ligands to probe the local interaction proficiencies. The comparison between binding energies and V-S(r) shows that the lowest minimum (V-S,V-min) and highest maximum (V-S,V-max) of V-S(r) on each particle can predict the most favorable binding site for the Lewis acids and base, respectively. V(S,min )can also rank the different binding strengths of Na+ and HF with the nanoparticles. For H2O, the binding strength versus V-S,V-max correlation is better for Ni-12 than for the Pt nanoparticles. This observation is discussed in relation to charge transfer/polarization and structural deformation upon interaction. In light of our findings, we compare the catalytic potential of Ni to the less abundant but more commonly used Pt.

Place, publisher, year, edition, pages
AMER CHEMICAL SOC, 2020
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:kth:diva-278925 (URN)10.1021/acs.jpcc.0c03714 (DOI)000550763500031 ()2-s2.0-85089276815 (Scopus ID)
Note

QC 20201118

Available from: 2020-11-18 Created: 2020-11-18 Last updated: 2022-06-25Bibliographically approved
Izquierdo, J., Demurget, N., Landa, A., Brinck, T., Mercero, J. M., Dinér, P., . . . Palomo, C. (2019). Asymmetric Synthesis of Adjacent Tri- and Tetrasubstituted Carbon Stereocenters: Organocatalytic Aldol Reaction of an Hydantoin Surrogate with Azaarene 2-Carbaldehydes. Chemistry - A European Journal
Open this publication in new window or tab >>Asymmetric Synthesis of Adjacent Tri- and Tetrasubstituted Carbon Stereocenters: Organocatalytic Aldol Reaction of an Hydantoin Surrogate with Azaarene 2-Carbaldehydes
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2019 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765Article in journal (Refereed) Published
Abstract [en]

A bifunctional amine/squaramide catalyst promoted direct aldol addition of an hydantoin surrogate to pyridine 2-carbaldehyde N-oxides to afford adducts bearing two vicinal tertiary/quaternary carbons in high diastereo- and enantioselectivity (d.r. up to >20:1; ee up to 98 %) is reported. Acid hydrolysis of adducts followed by reduction of the N-oxide group yields enantiopure carbinol-tethered quaternary hydantoin-azaarene conjugates with densely functionalized skeletons. DFT studies of the potential energy surface (B3LYP/6-31+G(d)+CPCM (dichloromethane)) of the reaction correlate the activity of different catalysts and support an intramolecular hydrogen-bond-assisted activation of the squaramide moiety in the transition state of the catalytic reaction.

Place, publisher, year, edition, pages
WILEY-V C H VERLAG GMBH, 2019
Keywords
asymmetric catalysis, azaarenes, Bronsted bases, hydantoins, quaternary stereocenters
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-261019 (URN)10.1002/chem.201902817 (DOI)000484834700001 ()31318987 (PubMedID)2-s2.0-85072225163 (Scopus ID)
Note

QC 20191010

Available from: 2019-10-10 Created: 2019-10-10 Last updated: 2022-06-26Bibliographically approved
Brinck, T. & Nyberg Borrfors, A. (2019). Electrostatics and polarization determine the strength of the halogen bond: a red card for charge transfer. Journal of Molecular Modeling, 25(5), Article ID 125.
Open this publication in new window or tab >>Electrostatics and polarization determine the strength of the halogen bond: a red card for charge transfer
2019 (English)In: Journal of Molecular Modeling, ISSN 1610-2940, E-ISSN 0948-5023, Vol. 25, no 5, article id 125Article in journal (Refereed) Published
Abstract [en]

A series of 20 halogen bonded complexes of the types R-Br center dot center dot center dot Br- (R is a substituted methyl group) and R '-CC-Br center dot center dot center dot Br- are investigated at the M06-2X/6-311+G(d,p) level of theory. Computations using a point-charge (PC) model, in which Br- is represented by a point charge in the electronic Hamiltonian, show that the halogen bond energy within this set of complexes is completely described by the interaction energy (E-PC) of the point charge. This is demonstrated by an excellent linear correlation between the quantum chemical interaction energy and E-PC with a slope of 0.88, a zero intercept, and a correlation coefficient of R-2=0.9995. Rigorous separation of E-PC into electrostatics and polarization shows the high importance of polarization for the strength of the halogen bond. Within the data set, the electrostatic interaction energy varies between 4 and-18kcal mol(-1), whereas the polarization energy varies between -4 and-10kcal mol(-1). The electrostatic interaction energy is correlated to the sum of the electron-withdrawing capacities of the substituents. The polarization energy generally decreases with increasing polarizability of the substituents, and polarization is mediated by the covalent bonds. The lower (more favorable) E-PC of CBr4---Br- compared to CF3Br center dot center dot center dot Br- is found to be determined by polarization as the electrostatic contribution is more favorable for CF3Br center dot center dot center dot Br-. The results of this study demonstrate that the halogen bond can be described accurately by electrostatics and polarization without any need to consider charge transfer.

Place, publisher, year, edition, pages
Springer Nature, 2019
Keywords
Halogen bonding, Electrostatic potential, Induction, Charge transfer, Energy decomposition, Sigma-hole
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-251273 (URN)10.1007/s00894-019-4014-7 (DOI)000465614200004 ()31020416 (PubMedID)2-s2.0-85064683551 (Scopus ID)
Note

QC 20220412

Available from: 2019-05-14 Created: 2019-05-14 Last updated: 2024-03-18Bibliographically approved
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ORCID iD: ORCID iD iconorcid.org/0000-0003-2673-075X

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