@article{pauly_white_deegbey_fosu_keller_mcguigan_dianat_gabilondo_wong_murphey_et al._2024, title={Coordination of copper within a crystalline carbon nitride and its catalytic reduction of CO<sub>2</sub>}, volume={3}, ISSN={["1477-9234"]}, DOI={10.1039/d4dt00359d}, abstractNote={Crystallites of Cu-coordinated poly(triazine imide) were synthesized by flux methods and deposited from particle suspensions onto electrodes, yielding sizable current densities for the electrocatalytic reduction of CO2.}, journal={DALTON TRANSACTIONS}, author={Pauly, Magnus and White, Ethan and Deegbey, Mawuli and Fosu, Emmanuel Adu and Keller, Landon and Mcguigan, Scott and Dianat, Golnaz and Gabilondo, Eric and Wong, Jian Cheng and Murphey, Corban G. E. and et al.}, year={2024}, month={Mar} }
 @article{mcguigan_tereniak_donley_smith_jeon_zhao_sampaio_pauly_keller_collins_et al._2023, title={Discovery of a Hybrid System for Photocatalytic CO<sub>2</sub> Reduction via Attachment of a Molecular Cobalt-Quaterpyridine Complex to a Crystalline Carbon Nitride}, volume={10}, ISSN={["2574-0962"]}, DOI={10.1021/acsaem.3c01670}, abstractNote={While recent reports have demonstrated the attachment of molecular catalysts to amorphous, graphitic carbon nitrides (g-CN) for light-driven CO2 reduction, approaches to the utilization of crystalline carbon nitrides have remained undiscovered. Herein, a functional hybrid photocatalyst system has been found using a crystalline carbon nitride semiconductor, poly(triazine imide) lithium chloride (PTI-LiCl), with a surface-attached CoCl2(qpy-Ph-COOH) catalyst for CO2 reduction. The molecular catalyst attaches to PTI-LiCl at concentrations from 0.10 to 4.30 wt % and exhibits ∼96% selectivity for CO production in a CO2-saturated, aqueous 0.5 M KHCO3 solution. Optimal loadings were found to be within 0.42–1.04 wt % with rates between 1,400 and 1,550 μmol CO/g·h at an irradiance of 172 mW/cm2 (λ = 390 nm) and apparent quantum yields of ∼2%. This optimized loading is postulated to represent a balance between maximal turnover frequency (TOF; 300+ h–1) and excess catalyst that can limit excited-electron lifetimes, as probed via transient absorption spectroscopy. An increase in the incident irradiance yields a concomitant increase in the TOFs and CO rates only for the higher catalyst loadings, reaching up to 2,149 μmol CO/g·h with a more efficient use of the catalyst surface capacity. The lower catalyst loadings, by comparison, already function at maximal TOFs. Higher surface loadings are also found to help mitigate deactivation of the molecular catalysts during extended catalytic testing (>24 h) owing to the greater net surface capacity for CO2 reduction, thus representing an effective strategy to extend lifetime. The hybrid particles can be deposited onto an FTO substrate to yield ∼60% Faradaic efficiency for photoelectrochemical CO production at −1.2 V vs Ag/AgCl bias. In summary, these results demonstrate the synergistic combination of a crystalline carbon nitride with a molecular catalyst that achieves among the highest known rates in carbon-nitride systems for the light-driven CO2 reduction to CO in aqueous solution with >95% selectivity.}, journal={ACS APPLIED ENERGY MATERIALS}, author={McGuigan, Scott and Tereniak, Stephen J. and Donley, Carrie L. and Smith, Avery and Jeon, Sungho and Zhao, Fengyi and Sampaio, Renato N. and Pauly, Magnus and Keller, Landon and Collins, Leonard and et al.}, year={2023}, month={Oct} }
 @article{cypher_pauly_castro_donley_maggard_goldberg_2023, title={Ethanol Upgrading to n-Butanol Using Transition-Metal-Incorporated Poly(triazine)imide Frameworks}, volume={15}, ISSN={["1944-8252"]}, DOI={10.1021/acsami.3c07396}, abstractNote={The upgrading of ethanol to n-butanol was performed using a molecular catalyst integrated into a carbon nitride support, one of the first examples of a supported molecular catalyst performing the Guerbet process. Initial studies using crystalline poly(triazine)imide (PTI) with lithium or transition-metal cations imbedded in the support together with a base as the catalyst system did not produce any significant amounts of n-butanol. However, when using the catalyst material formed by treatment of PTI-LiCl with [(Cp*)IrCl2]2 (Cp* = pentamethylcyclopentadienyl) along with sodium hydroxide, a 59% selectivity for butanol (13% yield) was obtained at 145 °C. This PTI-(Cp*)Ir material exhibited distinct UV-vis absorption features and powder X-ray diffractions which differ from those of the parent PTI-LiCl and [(Cp*)IrCl2]2. The PTI-(Cp*)Ir material was found to have a metal loading of 27% iridium per empirical unit of the framework. Along with the formation of n-butanol from the Guerbet reaction, the presence of higher chain alcohols was also observed.}, number={30}, journal={ACS APPLIED MATERIALS & INTERFACES}, author={Cypher, Sabrine M. and Pauly, Magnus and Castro, Leslie G. and Donley, Carrie L. and Maggard, Paul A. and Goldberg, Karen I.}, year={2023}, month={Jul}, pages={36384–36393} }
 @article{genoux_pauly_rooney_choi_shang_mcguigan_fataftah_kayser_suhr_debeer_et al._2023, title={Well-Defined Iron Sites in Crystalline Carbon Nitride}, volume={145}, ISSN={["1520-5126"]}, DOI={10.1021/jacs.3c05417}, abstractNote={Carbon nitride materials can be hosts for transition metal sites, but Mössbauer studies on iron complexes in carbon nitrides have always shown a mixture of environments and oxidation states. Here we describe the synthesis and characterization of a crystalline carbon nitride with stoichiometric iron sites that all have the same environment. The material (formula C6N9H2Fe0.4Li1.2Cl, abbreviated PTI/FeCl2) is derived from reacting poly(triazine imide)·LiCl (PTI/LiCl) with a low-melting FeCl2/KCl flux, followed by anaerobic rinsing with methanol. X-ray diffraction, X-ray absorption and Mössbauer spectroscopies, and SQUID magnetometry indicate that there are tetrahedral high-spin iron(II) sites throughout the material, all having the same geometry. The material is active for electrocatalytic nitrate reduction to ammonia, with a production rate of ca. 0.1 mmol cm-2 h-1 and Faradaic efficiency of ca. 80% at -0.80 V vs RHE.}, number={38}, journal={JOURNAL OF THE AMERICAN CHEMICAL SOCIETY}, author={Genoux, Alexandre and Pauly, Magnus and Rooney, Conor L. and Choi, Chungseok and Shang, Bo and McGuigan, Scott and Fataftah, Majed S. and Kayser, Yves and Suhr, Simon C. B. and Debeer, Serena and et al.}, year={2023}, month={Sep}, pages={20739–20744} }
 @article{shang_zhao_choi_jia_pauly_wu_tao_zhong_harmon_maggard_et al._2022, title={Monolayer Molecular Functionalization Enabled by Acid-Base Interaction for High-Performance Photochemical CO2 Reduction}, volume={6}, ISSN={["2380-8195"]}, DOI={10.1021/acsenergylett.2c01147}, abstractNote={We report the development of a hybrid catalyst consisting of carbon nitride (CNx) and cobalt phthalocyanine tetracarboxylic acid (CoPc-COOH), which converts CO2 to CO with high reaction rate (1067 μmol/g·h) and high selectivity (over 98%), under simulated solar irradiation. The carboxylic acid substituents on the phthalocyanine ligands play a critical role as they bind to the amine groups of CNx to enable nearly ideal monolayer coverage of the molecular cocatalyst on the semiconductor surface and promote catalytic activity from the molecular complex. Specifically, the CNx/CoPc-COOH hybrid material achieves a reaction rate 16 times higher than a CNx material containing unsubstituted CoPc molecules. We further show that activation and deactivation of the CNx/CoPc-COOH composite, which are associated with the reduction and decomposition of CoPc-COOH, respectively, both proceed at a nearly constant rate regardless of the CO2 reduction reaction rate. The decoupling of charge carrier injection and CO2 reduction catalysis has important mechanistic implications for future performance optimization and materials design of photocatalysts for CO2 reduction.}, journal={ACS ENERGY LETTERS}, author={Shang, Bo and Zhao, Fengyi and Choi, Chungseok and Jia, Xiaofan and Pauly, Magnus and Wu, Yueshen and Tao, Zixu and Zhong, Yiren and Harmon, Nia and Maggard, Paul A. and et al.}, year={2022}, month={Jun} }
 @article{pauly_kroeger_duppel_murphey_cahoon_lotsch_maggard_2022, title={Unveiling the complex configurational landscape of the intralayer cavities in a crystalline carbon nitride}, volume={2}, ISSN={["2041-6539"]}, DOI={10.1039/d1sc04648a}, abstractNote={The layered carbon nitride, poly(triazine imide), exhibits a complex configurational landscape for the coordination of cations within its intralayer cavities that has been elucidated for the first time.}, journal={CHEMICAL SCIENCE}, author={Pauly, Magnus and Kroeger, Julia and Duppel, Viola and Murphey, Corban and Cahoon, James and Lotsch, Bettina V and Maggard, Paul A.}, year={2022}, month={Feb} }