Development of sample preparation technique to characterize chemical structure of humin by synchrotron‐radiation–based X‐ray photoelectron spectroscopy

Carbon-binding state of humin (HM, a non-conductive insoluble organo-mineral humic substance) was successfully characterized for the first time by synchrotron-radiation-based X-ray photoelectron spectroscopy (XPS). Four sample preparation techniques-HM on double-sided carbon tape, indium sheet, copper mesh, and in pellet formed from the mixture of HM and copper powder (Cu) at different mixing ratios (1:1, 1:2, and 1:6 v/v)-were compared. The results show that HM samples prepared using the first three methods had significant charge buildup, which made the interpretation of the XPS spectra impossible because of the shifts in the binding energy of C 1s XPS spectra. Pellets of HM:Cu mixture enhanced the electrical conductivity and reduced charge buildup on the sample surface. Pellets prepared with HM:Cu ratio of 1:1 (v/v) provided the minimum charge buildup and high sensitivity with difference in C 1s spectra regardless of the observing position. The C 1s spectra, estimated by the subtraction of the carbon contamination in Cu, showed the resolution of C(sic)C (284.0 eV), C-C/C-H (285.1 eV), C-O (286.3 eV), C(sic)O (287.3 eV), and O(sic)C-O (288.3 eV) and three additional peaks of CF (289.3 eV), CF2 (290.2 eV), and CF3 (291.4 eV). Soft X-ray absorption spectroscopic (XAS) analysis further proved the existence of fluoride (F 1s) in HM structure. The detection of fluorinated carbon in HM showed a great advancement of XPS compared with other conventional analyses. X-ray with the incident angle of 0 degrees provided the smallest (nearly negligible) energy shift in the C 1s spectra of HM and did not damage the surface of the sample.