A review on g-C3N4-based photocatalysts

Semiconductor polymeric graphitic carbon nitride (g-C3N4) photocatalysts have attracted dramatically growing attention in the field of the visible-light-induced hydrogen evolution reaction (HER) because of their facile synthesis, easy functionalization, attractive electronic band structure, high physicochemical stability and photocatalytic activity. This review article presents a panorama of the latest advancements in the rational design and development of g-C3N4 and g-C3N4-based composite photocatalysts for HER application. Concretely, the review starts with the development history, synthetic strategy, electronic structure and physicochemical characteristics of g-C3N4 materials, followed by the rational design and engineering of various nanostructured g-C3N4 (e.g. thinner, highly crystalline, doped, and porous g-C3N4) photocatalysts for HER application. Then a series of highly efficient g-C3N4 (e.g., metal/g-C3N4, semiconductor/g-C3N4, metal organic framework/g-C3N4, carbon/g-C3N4, conducting polymer/g-C3N4, sensitizer/g-C3N4) composite photocatalysts are exemplified. Lastly, this review provides a comprehensive summary and outlook on the major challenges, opportunities, and inspiring perspectives for future research in this hot area on the basis of pioneering works. It is believed that the emerging g-C3N4-based photocatalysts will act as the “holy grail” for highly efficient photocatalytic HER under visible-light irradiation.

Semiconductor polymeric graphitic carbon nitride photocatalysts: the “holy grail” for the photocatalytic hydrogen evolution reaction under visible light

We demonstrate first room temperature, and ultrabright single photon emission from a color center in two-dimensional multilayer hexagonal boron nitride. Density Functional Theory calculations indicate that vacancy-related centers are a likely source of the emission.

/pdf/quantum-emission-from-hexagonal-boron-nitride-monolayers-2z38kw7vb8.pdf

Quantum emission from hexagonal boron nitride monolayers

Based on the concept of band bending at metal/semiconductor interfaces as an energy filter for electrons, we present a theory for the enhancement of the thermoelectric properties of semiconductor materials with metallic nanoinclusions. We show that the Seebeck coefficient can be significantly increased due to a strongly energy-dependent electronic scattering time. By including phonon scattering, we find that the enhancement of $ZT$ due to electron scattering is important for high doping, while at low doping it is primarily due to a decrease in the phonon thermal conductivity.

/pdf/theory-of-enhancement-of-thermoelectric-properties-of-2rvreb7dv1.pdf

Theory of enhancement of thermoelectric properties of materials with nanoinclusions.

Constructing a TiO2 based heterostructure is a very effective strategy for enhancing photocatalytic performance. The details of the electronic structure, interfacial interaction, and photogenerated carrier separation are important for explaining the photocatalytic properties of a heterostructure. Herein, the density of states, charge distribution, and the band offset of the monolayer g-C3N4/TiO2 heterojunction are systematically investigated through the hybrid DFT method. Results indicated that the valence band offset and the conduction band offset of the g-C3N4/TiO2 heterostructure were 0.40 and 0.18 eV, respectively. Interfacial interaction made the TiO2 surface with negative charge, whereas the g-C3N4 surface with positive charge, which led to the formation of a built-in electric field at the interface. Under illumination, the built-in electric field accelerates the transfer of photoexcited electrons in the CB of TiO2 into the VB of g-C3N4, thus resulting in the photoexcited electrons and holes naturally accumulating in the CB of g-C3N4 and the VB of TiO2, respectively. The photoexcited electrons and holes gathering in different surface regions efficiently prolonged the lifetime of photogenerated carriers. Meanwhile, electrons in the CB of g-C3N4 and holes in the VB of TiO2 had a stronger redox ability. Therefore, g-C3N4/TiO2 is a direct Z-scheme photocatalyst, and the Z-scheme heterostructure mechanism can well explain the improved photocatalytic activity of the g-C3N4/TiO2 heterostructure.

/pdf/a-new-understanding-of-the-photocatalytic-mechanism-of-the-4gv2iusfr3.pdf

A new understanding of the photocatalytic mechanism of the direct Z-scheme g-C3N4/TiO2 heterostructure

Replacing sluggish oxygen evolution reaction (OER) with hydrazine oxidation reaction (HzOR) to produce hydrogen has been considered as a more energy-efficient strategy than water splitting. However, the relatively high cell voltage in two-electrode system and the required external electric power hinder its scalable applications, especially in mobile devices. Herein, we report a bifunctional P, W co-doped Co3N nanowire array electrode with remarkable catalytic activity towards both HzOR (−55 mV at 10 mA cm−2) and hydrogen evolution reaction (HER, −41 mV at 10 mA cm−2). Inspiringly, a record low cell voltage of 28 mV is required to achieve 10 mA cm−2 in two-electrode system. DFT calculations decipher that the doping optimized H* adsorption/desorption and dehydrogenation kinetics could be the underlying mechanism. Importantly, a self-powered H2 production system by integrating a direct hydrazine fuel cell with a hydrazine splitting electrolyzer can achieve a decent rate of 1.25 mmol h−1 at room temperature. While facile hydrazine oxidation could replace the sluggish H2O oxidation reaction in renewable H2 production, few bifunctional catalysts exist. Here, authors explore a dual-doping strategy for Co3N nanowires that bestows bifunctionality toward both hydrazine oxidation and H2 evolution catalysis.

/pdf/manipulating-dehydrogenation-kinetics-through-dual-doping-co-z2gzkbv39i.pdf

Manipulating dehydrogenation kinetics through dual-doping Co 3 N electrode enables highly efficient hydrazine oxidation assisting self-powered H 2 production

Electrochemical water splitting for H2 production is limited by the sluggish anode oxygen evolution reaction (OER), thus using hydrazine oxidation reaction (HzOR) to replace OER has received great attention. Here we report the hierarchical porous nanosheet arrays with abundant Ni3 N-Co3 N heterointerfaces on Ni foam with superior hydrogen evolution reaction (HER) and HzOR activity, realizing working potentials of -43 and -88 mV for 10 mA cm-2 , respectively, and achieving an industry-level 1000 mA cm-2 at 200 mV for HzOR. The two-electrode overall hydrazine splitting (OHzS) electrolyzer requires the cell voltages of 0.071 and 0.76 V for 10 and 400 mA cm-2 , respectively. The H2 production powered by a direct hydrazine fuel cell (DHzFC) and a commercial solar cell are investigated to inspire future practical applications. DFT calculations decipher that heterointerfaces simultaneously optimize the hydrogen adsorption free energy (ΔGH* ) and promote the hydrazine dehydrogenation kinetics. This work provides a rationale for advanced bifunctional electrocatalysts, and propels the practical energy-saving H2 generation techniques.

Artificial Heterointerfaces Achieve Delicate Reaction Kinetics towards Hydrogen Evolution and Hydrazine Oxidation Catalysis

The structural, electronic, and optical properties of a g-C3N4(001)/BiVO4(010) nanocomposite have been investigated using first-principles calculations. The results indicate that g-C3N4(001) can stably adsorb onto the BiVO4(010) surface, and it tends to form a regular wavy shape. The calculated band gap of the g-C3N4(001)/BiVO4(010) nanocomposite is narrower compared with that of BiVO4 or BiVO4(010), primarily due to the introduction of N 2p states near the Fermi level. The g-C3N4(001)/BiVO4(010) nanocomposite has a favorable type-II band alignment; thus, photoexcited electrons can be injected into the conduction band of g-C3N4(001) from the conduction band of BiVO4(010). The proper interface charge distribution facilitates carrier separation in the g-C3N4(001)/BiVO4(010) interface region. The electron injection and carrier separation can prevent the recombination of electron–hole pairs. The calculated absorption coefficients indicate an obvious redshift of the absorption edge, which is in good agreement with the experimental results. Our calculation results suggest that the g-C3N4(001)/BiVO4(010) nanocomposite has significant advantages for visible-light photocatalysis.

Enhanced visible-light photocatalytic activity of a g-C3N4/BiVO4 nanocomposite: a first-principles study

Replacing the sluggish anode reaction in water electrolysis with thermodynamically favorable hydrazine oxidation could achieve energy-efficient H2 production, while the shortage of bifunctional catalysts limits its scale development. Here, we presented the scalable one-pot synthesis of partially exposed RuP2 nanoparticle-decorated carbon porous microsheets, which can act as the superior bifunctional catalyst outperforming Pt/C for both hydrazine oxidation reaction and hydrogen evolution reaction, where an ultralow working potential of -70 mV and an ultrasmall overpotential of 24 mV for 10 mA cm-2 can be achieved. The two-electrode electrolyzer can reach 10 mA cm-2 with a record-low cell voltage of 23 mV and an ultrahigh current density of 522 mA cm-2 at 1.0 V. The DFT calculations unravel the notability of partial exposure in the hybrid structure, as the exposed Ru atoms are the active sites for hydrazine dehydrogenation, while the C atoms exhibit a more thermoneutral value for H* adsorption.

https://advances.sciencemag.org/content/advances/6/44/eabb4197.full.pdf

Partially exposed RuP2 surface in hybrid structure endows its bifunctionality for hydrazine oxidation and hydrogen evolution catalysis.

Realizing the Synergy of Interface Engineering and Chemical Substitution for Ni3N Enables its Bifunctionality Toward Hydrazine Oxidation Assisted Energy-Saving Hydrogen Production

Jihua Zhang

Papers

Manipulating dehydrogenation kinetics through dual-doping Co 3 N electrode enables highly efficient hydrazine oxidation assisting self-powered H 2 production

Artificial Heterointerfaces Achieve Delicate Reaction Kinetics towards Hydrogen Evolution and Hydrazine Oxidation Catalysis

Enhanced visible-light photocatalytic activity of a g-C3N4/BiVO4 nanocomposite: a first-principles study

Partially exposed RuP2 surface in hybrid structure endows its bifunctionality for hydrazine oxidation and hydrogen evolution catalysis.

Realizing the Synergy of Interface Engineering and Chemical Substitution for Ni3N Enables its Bifunctionality Toward Hydrazine Oxidation Assisted Energy-Saving Hydrogen Production