**1. Introduction**

Due to their sufficient combustion and release of less harmful substances during combustion, higher alcohols with 2–6 carbon atoms are regarded as a kind of clean energy [1]. In addition, due to the high octane number, higher alcohols can also be used as a high-quality fuel additive. After separation, a series of basic chemicals with very high economic value, such as ethanol, propanol, and butanol, can be obtained [2–4]. Currently, ethanol is mainly produced by fermentation and ethylene hydration, while other alcohols are refined from petroleum. Obviously, in the long run, the above synthesis routes for higher alcohol would be restricted by increasingly depleted petroleum and food [5]. Recently, the synthesis of higher alcohols from syngas has attracted much attention, while this process is usually restricted by the low selectivity to higher alcohols and the poor stability of the catalyst.

Nowadays, four kinds of catalysts for higher alcohol synthesis (HAS) from syngas have been reported. Among them, the Rh-based catalysts show good activity and superior selectivity to ethanol, while the high price of Rh limits its industrial applications [6,7]. The harsh reaction conditions usually restrict large-scale applications for Mo-based catalysts [8,9]. For modified methanol synthesis catalysts, the main product is still methanol [10,11]. Fortunately, modified Fischer–Tropsch catalysts, mainly the modified Co and modified Fe catalysts, exhibit good activity and high selectivity for HAS at milder reaction conditions. However, the modified Fe catalysts are more beneficial to the water gas shift reaction (WGSR), generating lots of CO2; and the typical Cu modified Co catalysts usually show poor stability because of the phase separation of cobalt and copper [12–14]. Therefore, it has become an important issue for researchers to explore new catalysts for HAS from syngas with better catalytic performance.

Recently, Ga-modified Co catalysts were reported and showed excellent catalytic performance for higher alcohol synthesis [15–17]. He et al. prepared a series of Co-Ga catalysts by using Co-Ga-LDHs (layered double hydroxides) and found that Ga was beneficial to the non-dissociative adsorption of CO [15,16]. Gao et al. reported that gallium oxide can reduce the reduction degree of CoO and generate some Co2+ in the reduced catalysts, which act as non-dissociative CO adsorption sites for HAS, resulting in the high selectivity to alcohols for the Ga-Co/AC catalyst [17]. While the stability of Co-Ga catalysts should be further improved.

Here, considering the good activity and high selectivity on Co-Ga catalysts, K doped Co-Ga catalysts are explored by the reduction of La1−xKxCo0.65Ga0.35O3. The results show that the addition of K modulates the composition of La-Ga-O, enhances the dispersion of Co, and adjusts the electronic structure of Co, and as a result the catalysts possess excellent catalytic performance. Typically, an outstanding selectivity of 43.6% to the higher alcohols, and a stable catalytic performance during the 200 h reaction can be obtained.
