Transition metal oxides are a great alternative to less expensive hydrogen evolution reaction (HER) catalysts. However, the lack of conductivity of these materials requires a conductor material to support them and improve the activity toward HER. On the other hand, carbon paste electrodes result in a versatile and cheap electrode with good activity and conductivity in electrocatalytic hydrogen production, especially when the carbonaceous material is agglomerated with ionic liquids. In the present work, an electrode composed of multi-walled carbon nanotubes (MWCNTs) and cobalt ferrite oxide (CoFe2O4) was prepared. These compounds were included on an electrode agglomerated with the ionic liquid N-octylpyridinium hexafluorophosphate (IL) to obtain the modified CoFe2O4/MWCNTs/IL nanocomposite electrode. To evaluate the behavior of each metal of the bimetallic oxide, this compound was compared to the behavior of MWCNTs/IL where a single monometallic iron or cobalt oxides were included (i.e., α-Fe2O3/MWCNTs/IL and Co3O4/MWCNTs/IL). The synthesis of the oxides has been characterized by X-ray diffraction (XRD), RAMAN spectroscopy, and field emission scanning electronic microscopy (FE-SEM), corroborating the nanometric character and the structure of the compounds. The CoFe2O4/MWCNTs/IL nanocomposite system presents excellent electrocatalytic activity toward HER with an onset potential of -270 mV vs. RHE, evidencing an increase in activity compared to monometallic oxides and exhibiting onset potentials of -530 mV and -540 mV for α-Fe2O3/MWCNTs/IL and Co3O4/MWCNTs/IL, respectively. Finally, the system studied presents excellent stability during the 5 h of electrolysis, producing 132 μmol cm-2 h-1 of hydrogen gas.

Colloidal quantum dots (QDs) hold great promise as building blocks in solar technologies owing to their remarkable photostability and adjustable properties through the rationale involving size, atomic composition of core and shell, shapes, and surface states. However, most high-performing QDs in solar conversion contain hazardous metal elements, including Cd and Pb, posing significant environmental risks. Here, a comprehensive review of heavy-metal-free colloidal QDs for solar technologies, including photovoltaic (PV) devices, solar-to-chemical fuel conversion, and luminescent solar concentrators (LSCs), is presented. Emerging synthetic strategies to optimize the optical properties by tuning the energy band structure and manipulating charge dynamics within the QDs and at the QDs/charge acceptors interfaces, are analyzed. A comparative analysis of different synthetic methods is provided, structure-property relationships in these materials are discussed, and they are correlated with the performance of solar devices. This work is concluded with an outlook on challenges and opportunities for future work, including machine learning-based design, sustainable synthesis, and new surface/interface engineering.

The long-term objective in the field of heterogeneous catalysis is to develop an enzyme-like catalytic pathway that can achieve exceptional catalytic performance even at low temperatures. Herein, we have demonstrated a heterogeneous oxidase-type catalysis on the ZnO-supported Ru clusters (Ru/ZnO) for efficient H2 generation from an aqueous solution of formaldehyde (HCHO) at low temperatures. Due to its unique reaction pathway, the Ru/ZnO catalysts exhibited a temperature-insensitive activity for H2 generation at the temperature of 15 to 45 °C. Remarkably, even at a low temperature of 5 °C, the Ru/ZnO catalysts still enabled an H2 generation rate of 13.8 mmol gcat-1 h-1 with a turnover frequency (TOF) of 1678 h-1. Additionally, instead of producing a CO2/CO molecule, the HCHO molecule underwent a transformation into formic acid and/or formate as the byproduct. This finding presents a novel class of heterogeneous catalysts to expand the potential application scenarios of liquid hydrogen storage and transportation systems.

The study objective was to field-validate the technical feasibility of a membrane- and adsorption-enhanced water gas shift reaction process employing a carbon molecular sieve membrane (CMSM)-based membrane reactor (MR) followed by an adsorptive reactor (AR) for pre-combustion CO2 capture. The project was carried out in two different phases. In Phase I, the field-scale experimental MR-AR system was designed and constructed, the membranes, and adsorbents were prepared, and the unit was tested with simulated syngas to validate functionality. In Phase II, the unit was installed at the test site, field-tested using real syngas, and a technoeconomic analysis (TEA) of the technology was completed. All project milestones were met. Specifically, (i) high-performance CMSMs were prepared meeting the target H2 permeance (>1 m3/(m2.hbar) and H2/CO selectivity of >80 at temperatures of up to 300 °C and pressures of up to 25 bar with a <10% performance decline over the testing period; (ii) pelletized adsorbents were prepared for use in relevant conditions (250 °C < T < 450 °C, pressures up to 25 bar) with a working capacity of >2.5 wt.% and an attrition rate of <0.2; (iii) TEA showed that the MR-AR technology met the CO2 capture goals of 95% CO2 purity at a cost of electricity (COE) 30% less than baseline approaches.

Mesoporous honeycomb iron titanate using a sol-gel, evaporation-induced self-assembly method is synthesized. A triblock copolymer, F127, serves as a structure-directing agents, with iron chloride and titanium (IV) isopropoxide as inorganic precursors. The strong intermolecular force of attraction among urea, metal precursors, and polymer led to the formation of the mesoporous honeycomb structure. The study of physicochemical properties using different techniques reveals the formation of microstructures with a remarkable degree of porosity. The amorphous iron titanate outperforms the photochemical generation of H2 due to its disorderly structural arrangement and incomplete crystal formation. The randomness on the structure provides more area for catalytic reaction by providing more contact with the reactant and superior light absorption capability. The high amount of hydrogen gas, 40.66 mmolg-1h-1, is observed in the investigation over 3 h of activity for the iron titanate honeycomb sample. This yield is a more significant amount compared to the obtained for the commercially available TiO2 (23.78 mmolg-1h-1). The iron titanate materials synthesized with low-cost materials and methods are very effective and have the potential for hydrogen generation.

Solar energy utilization is of great significance to current challenges of the energy crisis and environmental pollution, which benefit the development of the global community to achieve carbon neutrality goals. Hydrogen energy is also treated as a good candidate for future energy supply since its combustion not only supplies high-density energy but also shows no pollution gas. In particular, photocatalytic water splitting has attracted increasing research as a promising method for H2 production. Recently, single-atom (SA) photocatalysts have been proposed as a potential solution to improve catalytic efficiency and lower the costs of photocatalytic water splitting for H2 generation. Owing to the maximized atom utilization rate, abundant surface active sites, and tunable coordination environment, SA photocatalysts have achieved significant progress. This review reviews developments of advanced SA photocatalysts for H2 generation regarding the different support materials. The recent progress of titanium dioxide, metal-organic frameworks, two-dimensional carbon materials, and red phosphorus supported SA photocatalysts are carefully discussed. In particular, the material designs, reaction mechanisms, modulation strategies, and perspectives are highlighted for realizing improved solar-to-energy efficiency and H2 generation rate. This work will supply significant references for future design and synthesis of advanced SA photocatalysts.

Various literature studies (Table 6) have reported that dispersion of metal nanoparticles (NPs) on graphitic carbon nitride g-C3N4 (M/CN) has considerably improved the photocatalytic hydrogen yield. It is understood that metal NPs create active sites on the surface of CN and act as a cocatalyst. However, the precise changes induced by different metal NPs on the surface of CN still elude us. Here, we report a thorough understanding and comparison of the morphology, metal-support interactions, interfacial charge transfer kinetics, and band characteristics in different M/CN (M = Pt, Pd, Au, Ag, Cu) correlated with photocatalytic activity. Among all metals, Pt/CN was found to be the best performer both under sunlight and UV-visible irradiation. Under sunlight, maximum H2@ 2.7 mmol/h/g was observed over Pt/CN followed by Pd/CN > Au/CN > Ag/CN > Cu/CN ≈ CN. The present study revealed that among all metals, Pt formed superior interfacial contact with g-C3N4 as compared to other metals. The maximum Schottky barrier height (Φb,Pt) of 0.66 V was observed at Pt/CN followed by Φb,Au/CN (0.46 V) and Φb,Pd/CN (0.05 V). The presence of electron-deficient Pt in Pt-XPS, decrease in the intensity of d-DOS of Pt near the Fermi level in VB-XPS, increase in CB tail states, and cathodic shift in Vfb in MS plots sufficiently confirmed strong metal-support interactions in Pt/CN. Due to the SPR effect, Au and Ag NPs suffered from agglomeration and poor dispersion during photodeposition. Finely dispersed Pt NPs (2-4 nm, 53% dispersion) successfully competed with shallow/deep trap states and drove the photogenerated electrons to active metallic sites in a drastically reduced time period as investigated by femtosecond transient absorption spectroscopy. Typically, an interfacial electron transfer rate, KIET,avg, of 2.5 × 1010 s-1 was observed for Pt/CN, while 0.087 × 1010 s-1 was observed in Au/CN. Band alignment/potentials at M/CN Schottky junctions were derived and most favorable in Pt/CN with CB tail states much above the water reduction potential; however, in the case of Pd, these extend much below the H+/H2 potential and hence behave like deep trap states. Thus, in Pd/CN (τ0 = 4200 ps, 49%) and Ag/CN (3870 ps, 53%), electron deep trapping dominates over charge transfer to active sites. The present study will help in designing futuristic new cocatalyst-photocatalyst systems.

Transition metal (TM) single atom catalysts (SACs) are of great potential for photocatalytic H2 production because of their abundant catalytic active sites and cost-effectiveness. As a promising support material, red phosphorus (RP) based SACs are still rarely investigated. In this work, we have carried out systematic theoretical investigations by anchoring TM atoms (Fe, Co, Ni, Cu) on RP for efficient photocatalytic H2 generation. Our density functional theory (DFT) calculations have revealed that 3d orbitals of TM locate close to the Fermi level to guarantee efficient electron transfer for photocatalytic performances. Compared with pristine RP, the introduction of single atom TM on the surface exhibit narrowed bandgaps, resulting in easier spatial separation for photon-generated charge carriers and an extended photocatalytic absorption window to the NIR range. Meanwhile, the H2O adsorptions are also highly preferred on the TM single atoms with strong electron exchange, which benefits the subsequent water-dissociation process. Due to the optimized electronic structure, the activation energy barrier of water-splitting has been remarkably reduced in RP-based SACs, revealing their promising potential for high-efficiency H2 production. Our comprehensive explorations and screening of novel RP-based SACs will offer a good reference for further designing novel photocatalysts for high-efficiency H2 generation.

Hydrogen (H2 ) produced from renewables will have a growing impact on the global energy dynamics towards sustainable and carbon-neutral standards. The share of green H2 is still too low to meet the net-zero target, while the demand for high-quality hydrogen continues to rise. These factors amplify the need for economically viable H2 generation technologies. The present article aims at evaluating the existing technologies for high-quality H2 production based on solar energy. Technologies such as water electrolysis, photoelectrochemical and solar thermochemical water splitting, liquid metal reactors and plasma conversion utilize solar power directly or indirectly (as carbon-neutral electrons) and are reviewed from the perspective of their current development level, technical limitations and future potential.

Developing eco-friendly strategies to produce green fuel has attracted continuous and extensive attention. In this study, a novel gas-templating method was developed to prepare 2D porous S-doped g-C3N4 photocatalyst through simultaneous pyrolysis of urea (main g-C3N4 precursor) and ammonium sulfate (sulfur source and structure promoter). Different content of ammonium sulfate was examined to find the optimal synthesis conditions and to investigate the property-governed activity. The physicochemical properties of the obtained photocatalysts were analyzed by X-ray diffraction (XRD), field emission-scanning electron microscopy (FE-SEM), scanning transmission electron microscopy (STEM), specific surface area (BET) measurement, ultraviolet-visible light diffuse reflectance spectroscopy (UV/vis DRS), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL) spectroscopy and reversed double-beam photo-acoustic spectroscopy (RDB-PAS). The as-prepared S-doped g-C3N4 photocatalysts were applied for photocatalytic H2 evolution under vis irradiation. The condition-dependent activity was probed to achieve the best photocatalytic performance. It was demonstrated that ammonium sulfate played a crucial role to achieve concurrently 2D morphology, controlled nanostructure, and S-doping of g-C3N4 in a one-pot process. The 2D nanoporous S-doped g-C3N4 of crumpled lamellar-like structure with large specific surface area (73.8 m2 g-1) and improved electron-hole separation showed a remarkable H2 generation rate, which was almost one order in magnitude higher than that of pristine g-C3N4. It has been found that though all properties are crucial for the overall photocatalytic performance, efficient doping is probably a key factor for high photocatalytic activity. Moreover, the photocatalysts exhibit significant stability during recycling. Accordingly, a significant potential of S-doped g-C3N4 has been revealed for practical use under natural solar radiation.