**5. Experimental**

The CAT samples (Figure 13) were precisely unloaded from the plant and packed in vacuum at the same time. CATs served 1–4 years (Figure 13 c–f) were selected, and all accidentally deactivated CATs (Figure 13 g–l) only served for less than two years.

Experimental sets employed for laboratory sulfur tolerant WGS reaction over selected CATs were discussed in the above.

Scanning electron microscopy (SEM) were taken with a JEOL 840F scanning microscope instrument (JEOL, Peabody, USA). Elemental mapping employed a GeminiSEM 300 scanning microscope instrument (Zeiss, Jena, Germany). Samples were deposited onto dust free platform and treated with gold-spray to enhance the signal before analysis.

X-ray diffraction results were obtained with a PANalytical X'Pert PRO diffractometer (Malvern Panalytical, Royston, UK) using Cu Kα1 radiation in diffraction angle from 5◦ to 90◦ (2 theta angular range) and a scan rate of 0.8◦ min−<sup>1</sup> in 2θ.

Laser Raman spectra were recorded with a Perkin-Elmer Raman Station 400F Raman Spectrometer (Perkin Elmer, Waltham Mass, USA). Raman shifts were recorded between 50cm and 1250cm−<sup>1</sup> for all CATs or 1000 and 2050cm−<sup>1</sup> for selected coked CATs. Powder samples were hold with a piece of clean glass during scan. For D/G ratio calculation LapSpec (Version 5.58, Horiba, Kyoto, Japan) software was used in the peak matching and integration (Gaussian method).

**Figure 13.** CATs samples investigated (samples in photo were broken into powders for characterizations): (**a**) γ-Al2O3; (**b**) as-prepared; (**c**) 1 year served; (**d**) 2-years served; (**e**) 3-years served; (**f**) 4-years served; (**g**) As; (**h**) Cl; (**i**) water-soaked; (**j**) caked 1; (**k**) caked 2; (**l**) sintered.

Infrared spectra were obtained by a Bruker Tensor II FTIR spectrometer (Bruker, Santa Barbara, USA) in the wavenumber range of 4000–400 cm<sup>−</sup>1. Samples were mixed with KBr (sample/KBr = 1:50 in weight) and then pressed into pellets for measurements.
