Supporting Information: Synthesis of Boron Doped Carbon Nitride Solids and Their Use as Metal Free Catalyst for Aliphatic C-H Bond Oxidation

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1 Supporting Information: Synthesis of Boron Doped Carbon itride Solids and Their Use as Metal Free Catalyst for Aliphatic C-H Bond Oxidation Yong Wang, * Haoran Li, Jia Yao, Xinchen Wang, and Markus Antonietti H H H H Porphyrin Phthalocyanine idealized g-c 3 4 Scheme S. itrogen-enriched π-conjugated macrocyclic scaffolds. Scheme S. Molecular oxygen oxidation of substituted aromatics to ketone using CB 0.5 as metal free heterogeneous catalyst S

2 Table S. Photocatalytic activity of Pt/CB 0.05 and Pt/g-C 3 4 for the hydrogen evolution reaction with visible light. Entry H evolution rate (µ mol/h) λ > 40 nm g-c B a Reaction conditions see ref. 7. Table S. Conversion and selectivity of toluene oxidation over CB x catalysts. Entry Catalyst Conv. [%] Sel. [%] BA a CB >99.0 CB > CB 0..0 > CB Reaction conditions: toluene 0.8ml, H O (30% in water solution) 0.77ml, catalyst 50mg, acetonitrile 8ml, reaction temperature 50 o C, reaction time h. a BA=benzaldehyde. Table S3. Conversion and selectivity of toluene oxidation over CB x catalysts. Entry Catalyst Toluene Conv. [%] H O Sel. (%) a g-c CB CB a moles of produced benzaldehyde/moles of reacted H O * 00. S

3 Table S4. Effect of different solvents on the oxidation of toluene over CB x catalysts. Entry Solvent Conv. Sel. [%] BA a [%] Acetonitrile.3 >99.0 CH Cl 0-3 Pyridine 0-4 Acetone 5.5 > Ethyl acetate 0.5 >99.0 Reaction conditions: toluene 0.8ml, H O (30% in water solution) 0.77ml, catalyst 50mg, acetonitrile 8ml, reaction temperature 50 o C, reaction time h. a BA=benzaldehyde. Table S5. Effect of the amount of CB x catalysts. Entry Amount (mg) Conv. [%] Sel. [%] BA a 5 3. > > > >99.0 Reaction conditions: toluene 0.8ml, H O (30% in water solution) 0.77ml, catalyst CB 0.5, acetonitrile 8ml, reaction temperature 50 o C, reaction time h. a BA=benzaldehyde. S3

4 Supplementary Material (ESI) for Chemical Science Table S. Comparison of the catalytic results using different catalysts. Entry Catalyst Sel. [%] benzaldehyde Sel. [%] benzyl alcohol CB0.5 > a P450 enzyme <5% 95% 3b FeTPPCl8Cl 3.% 8.8% a S. Wikipedia, see a S. H. Hanioka, M. Hamamura, K. Kakino, H. Ogata, H. Jinno, A. Takahashi, T. ishimura, M. Ando, Xenobiotica, 995, 5, b S3. T. akano,. Agatsuman, S. Kodama, H. Kakuda, and D. Dolphin, Bull. Chem. Soc. Jpn., 99, 9, CB0.5 CB0.0 CB 0.05 g-c wavenumber ( cm-) CB0.5 ( Before used) Wavenumber ( cm-) (00) Intensity (a.u.) 4000 %Transmittance % Transmittance CB0.5 (After used in oxidation of toluene) fresh CB0.5 Used CB θ (degree) 0 Figure S. FTIR spectra and XRD patterns of CBx materials. S4 000

5 Supplementary Material (ESI) for Chemical Science g-c34 CB0.00 F(R) CB0.05 CB0.05 red shift CB0. CB0.5 CB0. CB Wavelength (nm) 7 (a) Temperature ( oc) Conversion of Toluene(%) Conversion of Toluene (%) Figure S. UV spectra of of CBx materials (b) Time (h) Figure S3. Influence of reaction temperature and time on toluene conversion (over CB0.5). Influence of reaction temperature and time on the toluene conversion over CB0.5 was investigated. The influence of reaction temperature was studied in the temperature range between 00 and 00 oc. Indeed, no reaction takes place at 00 oc and h reaction time. Figure S3a shows that the conversion increases quickly with temperature, while staying constant beyond a reaction temperature of 50oC. This is typical for the setting in of a secondary reaction consuming reactants, presumably the decomposition of HO by the catalyst into products other than benzaldehyde, e.g. oxygen. Figure S3b illustrates that the oxidation of toluene at temperature 50 oc is indeed finished after h, prolongation of the reaction time to 4 or h give no obviously increase in the conversion of toluene. S5