Decade Milestone Advancement of Defect-Engineered g-C_(3)N_(4) for Solar Catalytic Applications

Over the past decade, graphitic carbon nitride(g-C_(3)N_(4)) has emerged as a universal photocatalyst toward various sustainable carbo-neutral technologies. Despite solar applications discrepancy, g-C_(3)N_(4) is still confronted with a general fatal issue of insufficient supply of thermodynamically active photocarriers due to its inferior solar harvesting ability and sluggish charge transfer dynamics. Fortunately, this could be significantly alleviated by the “all-in-one” defect engineering strategy, which enables a simultaneous amelioration of both textural uniqueness and intrinsic electronic band structures. To this end, we have summarized an unprecedently comprehensive discussion on defect controls including the vacancy/non-metallic dopant creation with optimized electronic band structure and electronic density, metallic doping with ultraactive coordinated environment(M–N_(x), M–C_(2)N_(2), M–O bonding), functional group grafting with optimized band structure, and promoted crystallinity with extended conjugation π system with weakened interlayered van der Waals interaction. Among them, the defect states induced by various defect types such as N vacancy, P/S/halogen dopants, and cyano group in boosting solar harvesting and accelerating photocarrier transfer have also been emphasized. More importantly, the shallow defect traps identified by femtosecond transient absorption spectra(fs-TAS) have also been highlighted. It is believed that this review would pave the way for future readers with a unique insight into a more precise defective g-C_(3)N_(4) “customization”, motivating more profound thinking and flourishing research outputs on g-C_(3)N_(4)-based photocatalysis.

Defect and interface control on graphitic carbon nitrides/upconversion nanocrystals for enhanced solar hydrogen production

The effective utilization of solar energy for hydrogen production requires an abundant supply of thermodynamically active photo-electrons;however,the photocatalysts are generally impeded by insufficient light absorption and fast photocarrier recombination.Here,we report a multiple-regulated strategy to capture photons and boost photocarrier dynamics by devel-oping a broadband photocatalyst composed of defect engineered g-C_(3)N_(4)(DCN)and upconversion NaYF4:Yb^(3+),Tm^(3+)(NYF)nanocrystals.Through a precise defect engineering,the S dopants and C vacancies jointly render DCN with defect states to effectively extend the visible light absorption to 590 nm and boost photocarrier separation via a moderate electron-trapping ability,thus facilitating the subsequent re-absorption and utilization of upconverted photons/electrons.Importantly,we found a promoted interfacial charge polarization between DCN and NYF has also been achieved mainly due to Y-N interaction,which further favors the upconverted excited energy transfer from NYF onto DCN as verified both theoretically and experimentally.With a 3D architecture,the NYF@DCN catalyst exhibits a superior solar H2 evolution rate among the reported upconversion-based system,which is 19.3 and 1.5 fold higher than bulk material and DCN,respectively.This work provides an innovative strategy to boost solar utilization by using defect engineering and building up interaction between hetero-materials.

Multilayer black phosphorus as saturable absorber for an Er:Lu_(2)O_(3) laser at~3 μm

Multilayer black phosphorus(BP) nanoplatelets of different thicknesses were prepared by the liquid phase exfoliation method and deposited onto yttrium aluminum garnet substrates to form saturable absorbers(SAs). These were characterized with respect to their thickness-dependent saturable absorption properties at 3 μm. The BP-SAs were employed in a passively Q-switched Er:Lu_2O_3 laser at 2.84 μm. By using BP exfoliated in different solvents,stable pulses as short as 359 ns were generated at an average output power of up to 755 m W. The repetition rate in the experiment was 107 k Hz, corresponding to a pulse energy of 7.1 μJ. These results prove that BP-SAs have a great potential for optical modulation in the mid-infrared range.

g-C_3N_4 as a saturable absorber for the passively Q-switched Nd:LLF laser at 1.3 μm

Two-dimensional(2D) graphite carbon nitride(g-C_3N_4) nanosheets have been successfully used as a saturable absorber(SA) in a passively Q-switched Nd:LLF laser at 1.3 μm for the first time, to the best of our knowledge.Under an incident pump power of 9.97 W, the shortest pulse duration of 275 ns was acquired with output power of0.96 W and pulse repetition rate of 154 k Hz, resulting in a pulse energy of 6.2 μJ. In addition, the saturable absorption behaviors of zero-dimensional 12 nm g-C_3N_4 nanoparticles(g-C_3N_4-NPs) and three-dimensional ordered mesoporous g-C_3N_4(mpg-C_3N_4) were also observed, although their morphology and structure were quite different from 2D g-C_3N_4. The experimental results introduce the potential application of g-C_3N_4 nanomaterials as SAs in Q-switched lasers.