The solar-to-chemical energy conversion is promising to tackle sustainability challenges toward a global future. The production of H2 from sunlight represents an attractive alternative to the use of carboniferous fossil fuels to meet our energy demands. In this context, the water splitting reaction photocatalyzed by semiconductors that can be excited under visible or near-infrared light excitation represents an attractive route to the clean generation of H2. In this review, we present an overview of the most important concepts behind the H2 generation, from water splitting, promoted by semiconductor-based systems for readers that were recently introduced to the water splitting topic. Then, we present the main classes of photocatalysts based on semiconductors. For each class of semiconductors, we focused on the examples that lead to the highest activities towards the H2 production and discuss the operation principles, advantages, performances, limitations, and challenges. We cover metal oxides, sulfides, and nitrides. We also discuss strategies in which these materials are combined, including hybridization with metal nanoparticles, other semiconductors, and carbon dots, to achieve improved performances and circumvent the limitations of the individual counterparts.

In this work, composites based on carbon (1, 10 and 20 wt.%) interfaced with Fe3O4 (magnetite) have been studied as catalysts for the oxidation of aqueous sulfide. The composites were prepared by assembling cellulose nanocrystals surrounding Fe3O4 followed by a controlled thermal decomposition at 400, 600 and 800 ºC. Mössbauer, X-ray diffractometry (XRD), Raman, thermogravimetry (TG), elemental analysis CHN, scanning electron microscopy (SEM/EDS), Fourier transform infrared spectroscopy (FTIR) and potentiometric titration indicated that at 400 and 600 ºC the cellulose nanocrystals decompose to different carbon forms, i.e., films, filaments and particles attached to the Fe3O4 crystals. At higher temperature, i.e., 800 ºC, this carbon on the magnetite surface further reacted to produce Fe0. UV-Vis, Raman and electrospray ionization mass spectrometry (ESI-MS) measurements showed that these composites catalyze the oxidation of aqueous sulfide to convert S2-aq to polysulfides Sn2- (where n = 2-9) and also oxygen containing polysulfides HOSn-. Simple kinetic experiments showed very low sulfide oxidation activities for pure Fe3O4 and pure carbon. On the other hand, the composites, especially with 10% C obtained at 600 ºC, were remarkably active. These results are discussed in terms of a possible participation of oxygen based redox groups present on the carbon surface and an electron transfer from the carbon to the Fe3O4 phase.

Novos compósitos magnéticos anfifílicos foram preparados pelo crescimento de nanotubos e nanofibras de carbono contendo partículas magnéticas através de deposição química de vapor (CVD), utilizando etanol como fonte de carbono e lama vermelha (RM, subproduto do processo Bayer de produção de alumina) como suporte e catalisador. Monitoramento da reação CVD à temperatura programada (TPCVD), difração de raios X (XRD), espectroscopia Mössbauer, espectroscopia de energia dispersiva (EDS), espectroscopia Raman, termogravimetria (TG/DTA), análise elementar (CHN), determinação de área superficial (BET), microscopia eletrônica de varredura (SEM) e de transmissão (TEM) e medidas magnéticas mostraram que etanol reduz íons de ferro na RM para formar fases magnéticas, por exemplo Fe3O4 e Fe0, e depósitos de carbono (5-42 wt.%) na forma de nanotubos e nanofibras. A combinação de nanoestruturas hidrofóbicas de carbono com óxidos hidrofílicos de Al, Si e Ti presentes na lama vermelha produziu materiais anfifílicos com excelente interação com a interface água-óleo. Misturas de óleo de soja ou de decalina com água (completamente imiscíveis) foram emulsificadas facilmente na presença dos compósitos anfifílicos. Quando os compósitos foram adicionados a uma emulsão água-biodiesel estável, as partículas anfifílicas difundiram-se para a interface água- óleo. As partículas do compósito foram atraídas por ímãs e carregaram com elas as gotas de óleo, levando à completa desemulsificação e separação entre biodiesel e água.

New magnetic amphiphilic composites were prepared by the catalytic carbon vapor deposition (CVD) growth of carbon nanotubes and nanofibers using ethanol as carbon source and red mud waste (RM, a by-product of the Bayer process of alumina production) as catalyst and support. Temperature-programmed CVD (TPCVD), analyses by X-ray diffractometry (XRD), Mössbauer spectroscopy, energy dispersive X-ray spectroscopy (EDS), Raman spectroscopy, thermogravimetry (TG/DTA), elemental analysis (CHN), superficial area determination (BET), scanning (SEM) and transmission (TEM) electron microscopies and magnetic measurements showed that ethanol reduces the iron ions in the red mud to form magnetic phases, e.g., Fe3O4 and Fe0, and carbon deposits (5-42 wt.%), particularly nanotubes and nanofibers. The combination of the hydrophobic carbon nanostructures with the hydrophilic Al, Si and Ti oxides present in the RM produced amphiphilic materials with excellent interaction with the water-oil interface. Soybean oil or decalin mixtures with water (completely immiscible) were easily emulsified in the presence of the amphiphilic composites. When the composites were added to stable biodiesel-water emulsions, the amphiphilic particles diffused to the interface oil-water. These composite particles were attracted by a magnet, carrying the oil droplets with them and leading to the complete demulsification and separation of the biodiesel from the water.