Algal biomass-based zero-waste biorefinery for producing optically pure (R)-γ-valerolactone and carbonaceous electrodes applicable for energy storage devices

• Algal-biomass-derived ( R )-GVL production with perfect enantiomeric excess (>99.99) • LA was obtained from G. verrucosa through acidic hydrothermal conversion. • Chemoenzymatic reaction converted LA to ( R )-GVL via 4-HV. • Residual algal biomass was used to prepare anode for LiB via simple heat treatment. • The results can construct to viable zero-waste biorefinery and circular bioeconomy. Mankind is facing a severe climate crisis caused by fossil fuel-derived CO 2 emissions. Although biorefineries utilizing biomass have been considered the best option for carbon-neutrality, most biorefinery-derived products have not yet been promising for economic feasibility; various strategies have been developed to increase economic competitiveness, and zero-waste biorefineries are challenging options. Herein, we aim to develop an algal biomass-based zero-waste biorefinery for producing enantioselective ( R )-γ-valerolactone (( R )-GVL) and carbonaceous electrodes applicable for Li-ion batteries (LiBs). Various algal biomasses were hydrothermally oxidized to produce levulinic acid (LA) as an intermediate for producing ( R )-GVL, resulting that Gracilaria verrucosa was selected as feedstock. For the hydroxylation of G. verrucosa -derived LA to 4-hydroxyvaleric acid (4-HV), 3-hydroxybutyrate dehydrogenase (HBDH) was explored through genome mining and further engineered. The engineered HBDH successfully converted G. verrucosa -derived LA to 4-HV, which was subsequently lactonized under acidic conditions, resulting in optically pure ( R )-GVL. To our knowledge, this is the first report of the production of an algal biomass-derived enantioselective ( R )-GVL with a perfect enantiomeric excess (>99.99 %) that can be used as a precursor for more valuable biopharmaceuticals and bioplastics than biofuels. Furthermore, residual G. verrucosa after hydrothermal oxidation was used as a carbonaceous anode material for LIBs for the first time; hard carbon anodes, which were prepared through simple heat treatment (800 ℃, 3 h, argon atmosphere), exhibit good capacities of 231, 191, 133, 108, 97 and 86 mAh/g at 0.05, 0.1, 0.5, 1, 1.5, and 2 A/g, respectively. The results discussed herein can provide insights into zero-waste biorefineries applicable for diverse industrial fields (e.g., biopolymer, biopharmaceutical and energy storage) and contribute to the construction of closed-carbon-loops for coping with climate change.