A highly sensitive gas chromatograph for in situ and operando experiments on catalytic reactions

We describe an automated gas sampling and injection unit for a gas chromatograph (GC). It has specially been designed for low concentrations of products formed in catalytic in situ and operando experiments when slow reactions on single crystal models are investigated. The unit makes use of a buffer volume that is filled with gas samples from the reactor at a reduced pressure. The gas samples are then compressed by He to the injection pressure of 1000 mbar and pushed into two sample loops of the GC, without major intermixing with He. With an additional cryo trap at one of the GC column heads, the design aims at concentrating the gas samples and focusing the peaks. The performance is characterized by experiments on the Fischer-Tropsch synthesis, using H₂/CO mixtures (syngas) at 200 and 950 mbar and a Co(0001) single crystal sample as model catalyst. Chromatograms recorded during the reaction display sharp, well separated peaks of saturated and unsaturated C₁ to C₄ hydrocarbons formed by the reaction, whereas the syngas matrix only gives moderate signals that can be well separated from the product peaks. Detection and quantification limits of 0.4 and 1.3 ppb, respectively, have been achieved and turnover numbers as low as 10^-5 s^-1 could be measured. The system can be combined with all known analysis techniques used in in situ and operando experiments.