@article{64182,
  abstract     = {{Overcoming the slow kinetics of the oxygen evolution reaction at the anode is a key challenge for the production of hydrogen via electrolysis. This reaction operates at very positive potentials, where the electrocatalyst is exposed to highly oxidative conditions and prone to potential-dependent transformation of the near-surface region. While substantial evidence for such surface restructuring exists, its extent and relevance for the catalyst’s activity are unclear. We address this topic for the case of Co3O4, one of the best-known electrocatalysts exhibiting surface restructuring, by studies of epitaxial (111)-ordered electrodeposited films with combined operando X-ray surface diffraction and absorption spectroscopy, electrochemical impedance spectroscopy, and electrochemical measurements on rotating disk electrodes. Comparison of the as-prepared and annealed state of the same samples, which both are stable even under long-term oxygen evolution conditions, provides clear insight into the role of surface defects. Our results show that defect-free annealed Co3O4(111) surfaces are structurally stable over a wide potential range and hydroxylate via adsorption at surface oxygen and Co sites. Potential-induced surface restructuring of the Co3O4 lattice occurs only in the presence of surface defects, leading to the formation of the well-known nanometer-thick oxyhydroxide skin layer. The presence of this skin layer promotes oxygen evolution at low overpotentials but results in higher Tafel slopes. As a result, highly ordered Co3O4(111) surfaces are more active at high current densities than defective Co3O4 surfaces that undergo surface restructuring. These results highlight that strategies for catalyst surface defect engineering need to be application-oriented.}},
  author       = {{Scharf, Carl Hendric and Chandraraj, Alex and Dyk, Konrad and Stebner, Felix and Lepin, Sören and Tian, Jing and El Bergmi Byaz, Laila and Stettner, Jochim and Leppin, Christian and Kotova, Anastasiia and Reinke, Sebastian and Linnemann, Julia and Maroun, Fouad and Magnussen, Olaf M.}},
  issn         = {{2155-5435}},
  journal      = {{ACS Catalysis}},
  keywords     = {{electrocatalysis, oxygen evolution reaction, cobalt spinel, operando characterization}},
  publisher    = {{American Chemical Society (ACS)}},
  title        = {{{Role of Defects in Reversible Surface Restructuring and Activity of Co<sub>3</sub>O<sub>4</sub> Oxygen Evolution Electrocatalysts}}},
  doi          = {{10.1021/acscatal.5c08785}},
  year         = {{2026}},
}

@article{61982,
  abstract     = {{Doped Co3O4 nanoparticles are investigated via spectro-electrochemistry in the (pre-) oxygen evolution reaction (OER) regime by tracing the absorption signal of the Co3+ d–d transition under applied bias for getting insight into the catalysts activation and the formation of catalytically active phases. In the low potential regime up to 1.37 VRHE, a rise in the optical absorption signal of the [Co3+]oct d–d transition is observed and attributed to a structural change from [Co2+]tet to [Co3+]oct due to an electrochemically induced surface restructuring with water. For applied potentials higher than 1.37 VRHE an overall offset of the absorption spectra in the UV–vis range, equivalent to a darkening of the materials is detected. This is attributed to the formation of a CoOx(OH)y skin layer as supported by high-energy X-ray diffraction (HE-XRD) measurements. We found that the kinetics of the Co3+ states are heavily influenced by the type of dopant with V-doped Co3O4 exhibiting stable Co3+ states (>20 min) while the Mn-doped Co3O4 Co3+ states reduce within 36 s under reductive bias. We conclude that doping Co3O4 with transition metals affects the formation and potential-dependent thickness of the CoOx(OH)y skin layer as the catalytically active phase and the formation of long-time stable surface Co3+ states after activation in the first OER cycle.}},
  author       = {{Kampermann, L. and Klein, J. and Wagner, T. and Kotova, A. and Placke-Yan, C. and Yasar, A. and Jacobse, L. and Lasagna, S. and Leppin, Christian and Schulz, S. and Linnemann, Julia and Bergmann, A. and Roldan Cuenya, B. and Bacher, G.}},
  issn         = {{2155-5435}},
  journal      = {{ACS Catalysis}},
  keywords     = {{electrocatalysis, oxygen evolution reaction, cobalt spinel, operando characterization, spectroelectrochemistry}},
  number       = {{21}},
  pages        = {{18391--18403}},
  publisher    = {{American Chemical Society (ACS)}},
  title        = {{{Operando Analysis of the Pre-OER Activation of Metal-Doped Co<sub>3</sub>O<sub>4</sub> Nanoparticle Catalysts}}},
  doi          = {{10.1021/acscatal.5c03900}},
  volume       = {{15}},
  year         = {{2025}},
}

@article{46547,
  author       = {{Rogolino, Andrea and Filho, José B. G. and Fritsch, Lorena and Ardisson, José D. and da Silva, Marcos A. R. and Atta Diab, Gabriel Ali and Silva, Ingrid Fernandes and Moraes, Carlos André Ferreira and Forim, Moacir Rossi and Bauer, Matthias and Kühne, Thomas D. and Antonietti, Markus and Teixeira, Ivo F.}},
  issn         = {{2155-5435}},
  journal      = {{ACS Catalysis}},
  keywords     = {{Catalysis, General Chemistry, pc2-ressources, Computing Resources Provided by the Paderborn Center for Parallel Computing}},
  number       = {{13}},
  pages        = {{8662--8669}},
  publisher    = {{American Chemical Society (ACS)}},
  title        = {{{Direct Synthesis of Acetone by Aerobic Propane Oxidation Promoted by Photoactive Iron(III) Chloride under Mild Conditions}}},
  doi          = {{10.1021/acscatal.3c02092}},
  volume       = {{13}},
  year         = {{2023}},
}

@article{41001,
  abstract     = {{For entropic reasons, the synthesis of macrocycles via olefin ring-closing metathesis (RCM) is impeded by competing acyclic diene metathesis (ADMET) oligomerization. With cationic molybdenum imido alkylidene N-heterocyclic carbene (NHC) complexes confined in tailored ordered mesoporous silica, RCM can be run with macrocyclization selectivities up to 98% and high substrate concentrations up to 0.1 M. Molecular dynamics simulations show that the high conversions are a direct result of the proximity between the surface-bound catalyst, proven by extended X-ray absorption spectroscopy, and the surface-located substrates. Back-diffusion of the macrocycles decreases with decreasing pore diameter of the silica and is responsible for the high macrocyclization efficiency. Also, Z-selectivity increases with decreasing pore diameter and increasing Tolman electronic parameter of the NHC. Running reactions at different concentrations allows for identifying the optimum substrate concentration for each material and substrate combination.}},
  author       = {{Ziegler, Felix and Kraus, Hamzeh and Benedikter, Mathis J. and Wang, Dongren and Bruckner, Johanna R. and Nowakowski, Michał and Weißer, Kilian and Solodenko, Helena and Schmitz, Guido and Bauer, Matthias and Hansen, Niels and Buchmeiser, Michael R.}},
  issn         = {{2155-5435}},
  journal      = {{ACS Catalysis}},
  keywords     = {{Catalysis, General Chemistry}},
  number       = {{18}},
  pages        = {{11570--11578}},
  publisher    = {{American Chemical Society (ACS)}},
  title        = {{{Confinement Effects for Efficient Macrocyclization Reactions with Supported Cationic Molybdenum Imido Alkylidene <i>N</i>-Heterocyclic Carbene Complexes}}},
  doi          = {{10.1021/acscatal.1c03057}},
  volume       = {{11}},
  year         = {{2021}},
}

@article{41323,
  author       = {{Ziegler, Felix and Kraus, Hamzeh and Benedikter, Mathis J. and Wang, Dongren and Bruckner, Johanna R. and Nowakowski, Michal and Weißer, Kilian and Solodenko, Helena and Schmitz, Guido and Bauer, Matthias and Hansen, Niels and Buchmeiser, Michael R.}},
  issn         = {{2155-5435}},
  journal      = {{ACS Catalysis}},
  keywords     = {{Catalysis, General Chemistry}},
  number       = {{18}},
  pages        = {{11570--11578}},
  publisher    = {{American Chemical Society (ACS)}},
  title        = {{{Confinement Effects for Efficient Macrocyclization Reactions with Supported Cationic Molybdenum Imido Alkylidene <i>N</i>-Heterocyclic Carbene Complexes}}},
  doi          = {{10.1021/acscatal.1c03057}},
  volume       = {{11}},
  year         = {{2021}},
}

@article{62803,
  abstract     = {{The aim to produce highly active, selective, and long-lived electrocatalysts by design drives major research efforts toward gaining fundamental understanding of the relationship between material properties and their catalytic performance. Surface characterization tools enable to assess atomic scale information on the complexity of electrocatalyst materials. Advancing electrochemical methodologies to adequately characterize such systems was less of a research focus point. In this Review, we shed light on the ability to gain fundamental insights into electrocatalysis from a complementary perspective and establish corresponding design strategies. These may rely on adopting the perceptions and models of other subareas of electrochemistry, such as corrosion, battery research, or electrodeposition. Concepts on how to account for and improve mass transport, manage gas bubble release, or exploit magnetic fields are highlighted in this respect. Particular attention is paid to deriving design strategies for nanoelectrocatalysts, which is often impeded, as structural and physical material properties are buried in electrochemical data of whole electrodes or even devices. Thus, a second major approach focuses on overcoming this difference in the considered level of complexity by methods of single-entity electrochemistry. The gained understanding of intrinsic catalyst performance may allow to rationally advance design concepts with increased complexity, such as three-dimensional electrode architectures. Many materials undergo structural changes upon formation of the working catalyst. Accordingly, developing “precatalysts” with low hindrance of the electrochemical transformation to the active catalyst is suggested as a final design strategy.}},
  author       = {{Linnemann, Julia and Kanokkanchana, Kannasoot and Tschulik, Kristina}},
  issn         = {{2155-5435}},
  journal      = {{ACS Catalysis}},
  keywords     = {{electrocatalysis}},
  number       = {{9}},
  pages        = {{5318--5346}},
  publisher    = {{American Chemical Society (ACS)}},
  title        = {{{Design Strategies for Electrocatalysts from an Electrochemist’s Perspective}}},
  doi          = {{10.1021/acscatal.0c04118}},
  volume       = {{11}},
  year         = {{2021}},
}

@article{41015,
  author       = {{Benedikter, Mathis and Musso, Janis and Kesharwani, Manoj K. and Sterz, K. Leonard and Elser, Iris and Ziegler, Felix and Fischer, Felix and Plietker, Bernd and Frey, Wolfgang and Kästner, Johannes and Winkler, Mario and van Slageren, Joris and Nowakowski, Michał and Bauer, Matthias and Buchmeiser, Michael R.}},
  issn         = {{2155-5435}},
  journal      = {{ACS Catalysis}},
  keywords     = {{Catalysis, General Chemistry}},
  number       = {{24}},
  pages        = {{14810--14823}},
  publisher    = {{American Chemical Society (ACS)}},
  title        = {{{Charge Distribution in Cationic Molybdenum Imido Alkylidene <i>N</i>-Heterocyclic Carbene Complexes: A Combined X-ray, XAS, XES, DFT, Mössbauer, and Catalysis Approach}}},
  doi          = {{10.1021/acscatal.0c03978}},
  volume       = {{10}},
  year         = {{2020}},
}

@article{41327,
  author       = {{Benedikter, Mathis and Musso, Janis and Kesharwani, Manoj K. and Sterz, K. Leonard and Elser, Iris and Ziegler, Felix and Fischer, Felix and Plietker, Bernd and Frey, Wolfgang and Kästner, Johannes and Winkler, Mario and van Slageren, Joris and Nowakowski, Michal and Bauer, Matthias and Buchmeiser, Michael R.}},
  issn         = {{2155-5435}},
  journal      = {{ACS Catalysis}},
  keywords     = {{Catalysis, General Chemistry}},
  number       = {{24}},
  pages        = {{14810--14823}},
  publisher    = {{American Chemical Society (ACS)}},
  title        = {{{Charge Distribution in Cationic Molybdenum Imido Alkylidene <i>N</i>-Heterocyclic Carbene Complexes: A Combined X-ray, XAS, XES, DFT, Mössbauer, and Catalysis Approach}}},
  doi          = {{10.1021/acscatal.0c03978}},
  volume       = {{10}},
  year         = {{2020}},
}

@article{37951,
  author       = {{Liu, Xin and Longwitz, Lars and Spiegelberg, Brian and Tönjes, Jan and Beweries, Torsten and Werner, Thomas}},
  issn         = {{2155-5435}},
  journal      = {{ACS Catalysis}},
  keywords     = {{T3, CSSD}},
  number       = {{22}},
  pages        = {{13659--13667}},
  publisher    = {{American Chemical Society (ACS)}},
  title        = {{{Erbium-Catalyzed Regioselective Isomerization–Cobalt-Catalyzed Transfer Hydrogenation Sequence for the Synthesis of Anti-Markovnikov Alcohols from Epoxides under Mild Conditions}}},
  doi          = {{10.1021/acscatal.0c03294}},
  volume       = {{10}},
  year         = {{2020}},
}

@article{37958,
  author       = {{Longwitz, Lars and Spannenberg, Anke and Werner, Thomas}},
  issn         = {{2155-5435}},
  journal      = {{ACS Catalysis}},
  keywords     = {{T2, CSSD}},
  number       = {{10}},
  pages        = {{9237--9244}},
  publisher    = {{American Chemical Society (ACS)}},
  title        = {{{Phosphetane Oxides as Redox Cycling Catalysts in the Catalytic Wittig Reaction at Room Temperature}}},
  doi          = {{10.1021/acscatal.9b02456}},
  volume       = {{9}},
  year         = {{2019}},
}

@article{37960,
  author       = {{Stadler, Bernhard M. and Wulf, Christoph and Werner, Thomas and Tin, Sergey and de Vries, Johannes G.}},
  issn         = {{2155-5435}},
  journal      = {{ACS Catalysis}},
  keywords     = {{T4, CSSD}},
  number       = {{9}},
  pages        = {{8012--8067}},
  publisher    = {{American Chemical Society (ACS)}},
  title        = {{{Catalytic Approaches to Monomers for Polymers Based on Renewables}}},
  doi          = {{10.1021/acscatal.9b01665}},
  volume       = {{9}},
  year         = {{2019}},
}

@article{62105,
  author       = {{Longwitz, Lars and Steinbauer, Johannes and Spannenberg, Anke and Werner, Thomas}},
  issn         = {{2155-5435}},
  journal      = {{ACS Catalysis}},
  keywords     = {{T1, T3, T4, CSSD}},
  number       = {{1}},
  pages        = {{665--672}},
  publisher    = {{American Chemical Society (ACS)}},
  title        = {{{Calcium-Based Catalytic System for the Synthesis of Bio-Derived Cyclic Carbonates under Mild Conditions}}},
  doi          = {{10.1021/acscatal.7b03367}},
  volume       = {{8}},
  year         = {{2018}},
}

@article{37970,
  author       = {{Longwitz, Lars and Steinbauer, Johannes and Spannenberg, Anke and Werner, Thomas}},
  issn         = {{2155-5435}},
  journal      = {{ACS Catalysis}},
  keywords     = {{T1, T3, T4}},
  number       = {{1}},
  pages        = {{665--672}},
  publisher    = {{American Chemical Society (ACS)}},
  title        = {{{Calcium-Based Catalytic System for the Synthesis of Bio-Derived Cyclic Carbonates under Mild Conditions}}},
  doi          = {{10.1021/acscatal.7b03367}},
  volume       = {{8}},
  year         = {{2017}},
}

@article{41059,
  author       = {{Busser, G. Wilma and Mei, Bastian and Weide, Philipp and Vesborg, Peter C. K. and Stührenberg, Kai and Bauer, Matthias and Huang, Xing and Willinger, Marc-Georg and Chorkendorff, Ib and Schlögl, Robert and Muhler, Martin}},
  issn         = {{2155-5435}},
  journal      = {{ACS Catalysis}},
  keywords     = {{Catalysis, General Chemistry}},
  number       = {{9}},
  pages        = {{5530--5539}},
  publisher    = {{American Chemical Society (ACS)}},
  title        = {{{Cocatalyst Designing: A Regenerable Molybdenum-Containing Ternary Cocatalyst System for Efficient Photocatalytic Water Splitting}}},
  doi          = {{10.1021/acscatal.5b01428}},
  volume       = {{5}},
  year         = {{2015}},
}

@article{41247,
  author       = {{Rabeah, Jabor and Bauer, Matthias and Baumann, Wolfgang and McConnell, Ann E. C. and Gabrielli, William F. and Webb, Paul B. and Selent, Detlef and Brückner, Angelika}},
  issn         = {{2155-5435}},
  journal      = {{ACS Catalysis}},
  keywords     = {{Catalysis, General Chemistry}},
  number       = {{1}},
  pages        = {{95--102}},
  publisher    = {{American Chemical Society (ACS)}},
  title        = {{{Formation, Operation and Deactivation of Cr Catalysts in Ethylene Tetramerization Directly Assessed by Operando EPR and XAS}}},
  doi          = {{10.1021/cs300686m}},
  volume       = {{3}},
  year         = {{2012}},
}