The production of first generation biofuels relies on food crops such as sugar beet, sugar cane, corn, wheat and cassava as substrates for bioethanol; and vegetable oils and animal fats for bio­diesel. Although years of intense R&D have made methods of bioethanol production (typically using the yeast Saccharomyces cerevisiae) technologically mature, there remain some serious questions regarding its sustainability. The use of food crops as a source of carbohydrate feed­stocks by these processes requires high-quality agricultural land. The inevitable conflict be­tween the increasing diversion of crops or land for fuel rather than food production has been highlighted as one of the prime causes of rising global food prices. Furthermore, corn ethanol producers in the US, have historically enjoyed a 45-cent-a-gallon federal tax credit for years (which ended in early 2012), costing the government US$30.5 billion between 2005 to 2011, rais­ing questions about its economic competitiveness with gasoline [10, 11].

These arguments have stimulated the search for so-called second generation biofuels, which utilize non-food lignocellulose biomass such as wood, dedicated energy crops, agricultural residues and municipal solid wastes as feedstocks. Biomass consists of cellulose, hemicellulose and lignin, and the latter of which is extremely resistant to degradation. One approach to un­locking the potential in this abundant feedstock is to separate the lignin from the carbohydrate fraction of the biomass via extensive pre-treatment of the lignocellulose involving, for exam­ple, steam-explosion and/or acid hydrolysis. These pre-treatments are designed to allow the carbohydrate portion of the biomass to be broken down into simple sugars, for example by en­zymatic hydrolysis using exogenously added cellulases to release fermentable sugars [12]. Such approaches have been found to be expensive and rate limiting [6, 12, 13]. Alternatively, processes using cellulolytic microorganisms (such as C. cellulolyticum, C. thermocellum, and C. phytofermentans) to carry out both the hydrolysis of lignocelluloses and sugar fermentation in a single step, termed ‘Consolidated Bioprocessing Process (CBP)’ [12] have been proposed, how­ever the development of these is still at an early stage, and again low conversion rates seem to be a major limitation that needs to be overcome.

Microorganisms such as acetogens, carboxytrophs and methanogens are able to utilize the CO2 + H2, and/or CO available in such syngas as their sole source of carbon and energy for growth as well as the production of biofuels and other valuable products. However, only acetogens are described to synthesize metabolic end products that have potentials as liquid transportation fuels. While biological processes are generally considered slower than chemical reactions, the use of these microbes to carry out syngas fermentation offers several key advantages over alter­native thermo-chemical approaches such as the Fischer-Tropsch’ process (FTP). First, microbi­al processes operate at ambient temperatures and low pressures which offer significant energy and cost savings. Second, the ambient conditions and irreversible nature of biological reactions also avoid thermodynamic equilibrium relationships and allow near complete conversion effi­ciencies [14, 15]. Third, biological conversions are commonly more specific due to high enzy­matic specificities, resulting in higher product yield with the formation of fewer by-products. Fourth, unlike traditional chemical catalysts which require a set feed gas composition to yield desired product ratios or suite, microbial processes have freedom to operate for the production ofthe same suite of products across a wider range of CO:H2 ratios in the feed gas [16]. Fifth, bio­catalysts exhibit a much higher tolerance to poisoning by tars, sulphur and chlorine than inor­ganic catalysts [6, 16]. However, some challenges have been identified for syngas fermentation to be commercialized, including gas mass transfer limitations, long retention times due to slow cell growth, and lower alcohol production rates and broth concentrations. Recent progress and development to remedy these issues will be highlighted in this review.