Abstract: A highly selective and multifunctional electrocatalyst is constructed by combining a single-phase Ni3S2 obtained via pulsed laser ablation in liquids and different contents of 

nickel  tetraphenylporphyrin  (NiTPP) complex.  Catalytic  performance  is assessed  in consecutive hydrogen and oxygen evolution and benzyl alcohol oxidation reactions, in which 

the optimal NiS-NiTPP10% exhibits the highest activity with overpotentials of 435, 320, and 170  mV,  respectively.  Moreover,  NiS-NiTPP10%  favors alcohol  oxidation  reactions and 

produces benzoic acid at a yield rate of 2.23 mM h−1cm−2 with 100% mass balance, 98.3% Faradaic efficiency, and 99.8% selectivity. Finally, the system with simultaneous H2 evolution 

and value-added benzoic acid production is successfully employed in a NiS-NiTPP10%||NiS-NiTPP10% electrolyzer, resulting in a high Faradaic efficiency of 81% and 99% and yield 

rate of 0.42 and 4.03 mM h−1 cm−2, respectively, at a lower cell voltage of 193 mV than the standard water electrolyzer. The phenyl rings of NiTPP could act as the terminal for the 

benzyl alcohol molecule, and the high surface area of Ni3S2 could accelerate the oxidation process; hence, both Ni3S2 and NiTPP boost the performance of NiS-NiTPP10% via charge- 

density modulation and strong synergetic effects.