In the field of electrochemistry, two common chemical and structural changes are frequently observed: electrode activation and electrode degradation. The degree to which each process is explored varies, where the latter are often underexplored. Emphasis is often instilled on what makes the best catalysts great rather than why they fail. Herein, the activation and deactivation of select catalysts or catalytic interfaces are explored with the goals of producing catalysts for water electrolysis and recycling coenzymes while understanding how the catalysts fail during their catalytic processes. Followed by the introduction (Chapter 1), a biomimetic of the diiron hydrogenase active site, [FeFe], was covalently grafted onto a silicon photoelectrode (Chapter 2). It found that in the photoelectrochemical hydrogen evolution process, the active site was degraded with the cleavage of the diiron active site from its thiolate ligands. Similarly, the stability of a series of transition metal dichalcogenide (TMDC) catalysts, 2H-MoS2, 2H-WS2, and 2H-WSe2 were assessed under near-neutral conditions for regenerating the reduced form of nicotinamide adenine dinucleotide (1,4-NADH). The catalyst stability was dependent on, dissolved gas, electrolyte present in solution, and the crystallinity of the TMDC where dissolved oxygen, sulfate ions, and amorphous TMDCs structure accelerated their decomposition respectively. With thermal annealing, crystalline TMDCs could selectively and efficiently reduce the oxidized form of nicotinamide adenine dinucleotide (NAD+) to 1,4-NADH and 3-carbamyl-1-methylpyridinium chloride (MNA+), a biomimetic of NAD+, to 1-methyl-1,4-dihydropyridine-3-carboxamide (MNAH) at modest overpotentials (Chapter 4). Edge-rich TMDCs, when fabricated had a native oxide layer that can be identified by surface sensitive techniques. In addition, it was discovered that TMDCs could be activated by electrolysis, during which the oxide layer can be removed (Chapter 3 and Chapter 4). Further a thin film of TiO2 was used to improve the durability of NiFe layered double hydroxides (LDH) as an electrocatalyst for water oxidation in near neutral conditions (Chapter 5). While experimenting with LDH fabrication methods a facile mechano-chemical solvent-free method was developed that can produce a high-performing NiFe LDH, comparable to other reported LDH for water oxidation grown using time-consuming energy intensive methods.