Photocatalytic Application in Energy and Environmental Sustainability: Comparison
Please note this is a comparison between Version 1 by Zhiping Zhang and Version 2 by Amina Yu.

The energy and environmental crises have been an ongoing challenge, which is related to the vital interests of people around the globe. How to solve this problem through sustainable development strategies is considered deeply by scientific researchers. Photocatalysis provides a powerful technique for fully utilizing solar in the field of energy conversion.

  • g-C3N4
  • preparation
  • modification
  • hydrogen evolution
  • CO2 conversion

1. H2 Production

Hydrogen is gathering strong momentum as a pivotal energy transition pillar driven by the global shift toward decarbonization. Nevertheless, 85% of H2 is produced from fossil fuel combustion, which generates roughly 500 metric tons of carbon dioxide every year and proffers a challenge and obstacle toward the sustainable living of future generations [1][132]. Solar-driven photocatalytic H2 generation as a promising technology has received extensive attention in addressing the global energy crisis [2][3][133,134]. Photocatalytic water splitting for the energy transformation from solar to eco-friendly fuels has been studied for decades with various semiconductor photocatalysts. As a type of semiconductor photocatalyst, g-C3N4 is simple and inexpensive to fabricate, and has an adequate bandgap (≈2.7 eV) for activation upon sunlight irradiation. Wang’s group first utilized g-C3N4 in photocatalytic H2 evolution [4][5][15,135]. Nonetheless, pristine g-C3N4 is far from satisfactory energy conversion because of its low light energy utilization, low density active sites, and ineffective isolation of the photogenerated excitons. Thus, researchers have proposed numerous strategies to boost the photocatalytic activity of g-C3N4-based materials for H2 production. For example, the g-C3N4/carbon-dot-based nanocomposites, which possess enormous visible light absorption and applicable energy structures, have been prepared and serve as efficacious photocatalysts in photocatalytic water splitting for H2 generation under light illumination [3][6][7][8][128,134,136,137]. Gao et al. reported hexagonal tubular g-C3N4/CD-based nanocomposites which exhibited nine times higher than bulk g-C3N4 in H2 production rate [3][134] and related results indicated that CDs performed as both photosensitizer and electron acceptor. CDs could absorb long wavelength light to extend the visible-light response region and suppress the recombination of electron-hole pairs. Hussien et al. [9][138] combined four different strategies (non-metal doping, porosity generation, functionalization with amino groups, and thermal oxidation etching) in a one-pot thermal reaction and successfully prepared amino-functionalized ultrathin nanoporous B-doped g-C3N4 by using NH4Cl as a gas bubble template, together with a thermal exfoliation process to produce ultrathin sheets. According to the process, the surface area, adsorption capacity, and charge migration of the as-prepared photocatalyst have been improved, and a 3800 µmol g−1 h−1 H2 generation rate and 10.6% prominent quantum yield were recorded. Li et al. [10][139] decorated carbon self-doping g-C3N4 nanosheets with gold-platinum (AuPt) nanocrystals through a photo-deposition route and compared the photocatalytic H2 evolution performance of Pt/CCN, Au/CCN, Au/Pt/CCN, and Pt/Au/CCN, in which AuPt/CCN stood out and gave the highest H2 generation rate (1135 μmol h−1). The excellent performance can be ascribed to the non-plasmon-related synergistic effect of Au and Pt atoms in AuPt nanocrystals. Sun et al. [11][140] assessed the arrangements of metal- and non-metal-modified g-C3N4 composites in hydrogen evolution and found that the contribution of dye conjugation in non-metallic g-C3N4 composites favored their performance. However, the co-catalyst doping strategy was recommended for metallic g-C3N4 composites. In addition, the hybrid of MOF materials and g-C3N4 is also a good approach to develop novel photocatalysts. For example, Devarayapalli et al. [12][141] reported a g-C3N4/ZIF-67 nanocomposite and obtained a 2084 μmol g−1 H2 production, which is 3.84-fold greater than that of bare g-C3N4.

2. CO2 Photoreduction over g-C3N4

Rising atmospheric levels of CO2 and the consumption of fossil fuels raise a concern about the continued reliance on the utilization of fossil fuels for both energy and chemical production [13][173]. Photocatalytic reduction of CO2 is a promising strategy to meet increasing energy needs and reduce the greenhouse effect [14][174]. Through photocatalytic reduction, CO2 can be converted to light oxygenates and hydrocarbons. Photocatalytic CO2 reduction is a multielectron transfer process. Fu et al. [15][175] have listed the possible reaction and corresponding redox potentials and stated that CO2 was complicated to reduce at room temperature due to its stable chemical structure. For the complex reaction, five factors, comprising the matching of band energy, separation of charge carrier, kinetic of e- and hole transfer to CO2 and reductant, the basicity of photocatalyst, and the strength and coverage of CO2 adsorption, are considered to be crucial [16][176]. As a hot member of photocatalysts, g-C3N4 has been applied to CO2 photo-reduction in recent years because the CB of g-C3N4 is sufficient to reduce CO2 to various hydrocarbons, such as CH3OH, CH4, HCHO, and HCOOH, and so onetc. [17][177].
However, metal-free g-C3N4 is limited for CO2 reduction activity due to its poor ability to activate the C-O bond of CO2. To improve the photocatalytic movement of CO2 conversion, different metal units have been composited with g-C3N4 for broadening the absorption response range, and accelerating the charge separation and transfer, such as Pt/g-C3N4 [18][178], Co2+/g-C3N4 [19][20][179,180], Au/g-C3N4 [21][181], and so onetc. Metal nanoparticles acting as cocatalysts could effectively improve the photocatalytic activity and selectivity of CO2 reduction. In addition, other methods, including doping, loading cocatalysts and nanocarbons, constructing Z-scheme, and heterojunction, have also been employed [22][23][24][25][26][27][28][29][30][16,182,183,184,185,186,187,188,189]. For example, Fu et al. [31][190] prepared hierarchical porous O-doped g-C3N4 nanotubes (OCN-Tube) through continuing thermal oxidation exfoliation and curling condensation of bulk g-C3N4. Due to the higher specific surface area, better light harvesting, higher CO2 uptake capacity, and superior separation efficiency of photogenerated charge carriers, the OCN-Tube exhibits excellent photocatalytic CO2 reduction performance into CH3OH. The CH3OH evolution rate was as high as 0.88 µmol g−1 h−1, five times higher than the bulk (0.17 µmol g−1 h−1). Huo et al. [32][191] fabricated amine-modified step-scheme (S-scheme) porous g-C3N4/CdSe-diethylenetriamine (A-PCN/CdSe-DETA) by a one-step microwave hydrothermal method. The modification by amine and formation of S-scheme heterojunction contributed to the remarkable photocatalytic performance of A-PCN/CdSe-DETA composite in CO2 reduction and a CO production rate of 25.87 μmol/(h g) was achieved under visible-light irradiation. Wang et al. [14][174] reviewed different modification methods of g-C3N4-based photocatalysts for CO2 reduction. They discussed each method (including morphology adjustment, co-catalysts, heterostructures, and doping) and compared the theoretical calculations and experimental results. By morphology adjustment, g-C3N4 with various shapes can be fabricated, such as rods, tubes, nanosheets, hollow spheres, and honeycomb-like structures. Due to the advantage of cocatalysts (e.g., Au, Ag, Pt, Pd, MXene, AuCu alloy, Pd-Ag), g-C3N4 with co-catalysts can be widely applied to activate CO2 on the surface. Heterojunction with different types is also an effective method to improve the properties of g-C3N4-based materials. In addition, elemental doping is considered a common method to enhance photocatalytic quantum efficiency by changing the energy band, surface electronic property, and electrical conductivity.

3. Degradation of Organic Pollutants

Along with rapid population growth and significant industrialization development, large numbers of toxic, hazardous, and endless contaminants invade the environment, threatening to human life, especially a variety of pollutants present in water that are difficult to eliminate or degrade naturally. Photocatalytic degradation of contaminants is a green and efficient technology for coping with sewage [6][33][128,223]. Different kinds of g-C3N4-based materials (Table 1) have been exploited to increase the photodecomposition efficiency of pollutants, such as the constructed heterojunction, loading O2-reduction co-catalysts, g-C3N4/CDs-based nanocomposites, and so on [23][34][35][36][182,224,225,226]. Generally, under the irradiation of visible light, the photogenerated electrons (e) on the g-C3N4 catalyst will be excited from VB to CB, leaving holes (h+) in the VB. The holes can oxidize pollutants directly or react with H2O/OH to form hydroxyl radicals [37][227]. When the REDOX potential of g-C3N4 composites is more negative than O2/O2, the photogenerated electrons in the material can react with O2 to produce O2 with strong oxidation capacity [38][228]. In addition, the resulting O2 could be protonated to produce OH [39][229]. Finally, the RhB dye is degraded to CO2 and H2O under the action of these free radicals. Chen et al. [40][230] fabricated a BiFeO3/g-C3N4 heterostructure through mixing-calcining and compared its performance with BiFeO3. Around 30% higher photocatalytic efficiency toward RhB dye was observed for the BiFeO3/10% g-C3N4 heterostructure, which was assigned to the contribution of a higher concentration of O2. Zhang et al. [41][231] studied the selective reduction of molecular oxygen on g-C3N4 and probed its effect on the photocatalytic phenol degradation process. Compared with bulk g-C3N4, the exfoliated nanosheet yielded a three times improvement in photocatalytic phenol degradation. It has been demonstrated that bulk g-C3N4 prefers to reduce O2 to O2via one-electron reduction. At the same time, the photoexcited g-C3N4 nanosheet facilitates the two-electron reduction of O2 to yield H2O2 because of the formation of 1,4-endoperoxide species. The two-electron reduction of O2 on the nanosheet surface boosts hole generation and thus accelerates phenol oxidation degradation [41][42][231,232]. Thus, to improve the photocatalytic performance of g-C3N4, more effort should be devoted to strengthening the solid O2-reduction reactions. For example, Liu et al. [43][83] reported a heterojunction material of K-doped g-C3N4 nanosheet -CdS and degraded tetracycline with 94% degradation under visible light in 30 min. In addition, due to the electronegativities, ionic radius differences, and impurity states, element doping is also an effective method to manipulate the electronic structure and physicochemical performance of g-C3N4-based materials. Gao et al. [44][68] synthesized Fe-doped g-C3N4 nanosheets and obtained 1.4- and 1.7-fold higher degradation rates of MB than that of pure g-C3N4 nanosheets and bulk g-C3N4, which indicated that the exploitation of efficient g-C3N4-based photocatalysts with high stabilization and degradation under visible light irradiation would significantly contribute to sewage disposal. Zhang et al. [45][117] synthesized a novel hybrid of Zr-based metal-organic framework with g-C3N4 (UiO-66/g-C3N4) nanosheets and applied a photodegradation of methylene blue, by which a 100% photodegradation was achieved within 4 h under visible light. This Here, it has been research has provided with a new insight into the design of g-C3N4-based photocatalysts to deal with organic dyes in the environment.
Table 13.
Photocatalytic degradation of pollutants over g-C
3
N
4
-based materials reported within the last three years.
Entry Photocatalyst Pollutant Concentration Light Source Degradation

Efficiency/%
Ref.
1 5% g-C3N4-TiO2 Acetaminophen: 0.033 mM 300 W Xe (>400 nm) 99.3 in 30 min [46][233]
2 3ZIF/1.5Au-PCN Bisphenol A 350 W Xe (>420 nm) >85% [47][221]
3 Cu(tmpa)/20%CN Congo red: 100 mg·L−1 150 W Xe 98.2% in 3 min [48][234]
4 BiO-Ag(0)/C3N4@

ZIF-67
Congo red: 12 mg·L−1 Natural sunlight 90% in 150 min [49][13]
5 C3N4/RGO/Bi2Fe4O9 Congo red: 10 mg·L−1 LED 30 W 87.65% in 60 min [50][235]
6 g-C3N4/Co-MOF Crystal violet: 4 ppm MaX 303 solar simulator (50 mW/cm) 95% in 80 min [12][141]
7 Honeycomb-like

g-C3N4/CeO2-x
Cr (VI): 20 mg·L−1 300 W Xe (>420 nm) 98%

in 150 min
[51][236]
8 Sm6WO12/g-C3N4 Levofloxacin: 10 mg·L−1 150 Mw cm−2 tungsten lamp 98% in 70 min [52][237]
9 O-g/C3N4 Lincomycin: 100 mg·L−1 PCX50C system (>420 nm) 99% within 3 h [53][238]
10 ZnO-modified g-C3N4 Methylene blue: 10 ppm 200 W tungsten

lamp (>420 nm)
97% in 80 min [54][239]
11 Wood-like g-C3N4@WDC Methylene blue: 20 mg·L−1 300 W Xe (>400 nm) 98% in 60 min [55][240]
12 BiO-Ag(0)/C3N4@

ZIF-67
Methylene blue: 12 mg·L−1 Natural sunlight 96.5% in 120 min [49][13]
13 Cerium-based GO/g-C3N4/Fe2O3 Methylene blue: 10 mg·L−1 Light bulb 70.61% in 45 min [56][14]
14 Ytterbium oxide-based GO/g-C3N4/Fe2O3 Methylene blue: 10 mg·L−1 Light bulb 83.5% in 45 min [56][14]
15 Cu(tmpa)/20%CN Methylene blue: 10 mg·L−1 150W Xe 92.0% within 20 min [48][234]
16 C3N4x/AgOy@Co1-xBi1-yO7 Methylene blue: 25 mL 10 mM 100 W tungsten bulb 96.4% in 120 min [57][12]
17 Ternary composites of Zr-MOF combined with g-C3N4 and Ag3PO4 Methylene blue: 10 mg·L−1 85-watt tungsten lamp

outdoor/solar light in

an open air
95% within 240 93% within 105 min [58][241]
18 PSCN/Ag@AgI/WO3 Malachite green: 1 × 10 −4 mol dm−3 35 W LED 90% in 60 min [59][242]
19 Cu(tmpa)/20%CN Malachite green: 30 mg·L−1 150W Xe 92.9% in 35 min [48][234]
20 20% g-C3N4/Bi4O5I2 Methyl orange: 20 mg·L−1 350 W Xe 0.164 min−1 [60][243]
21 Cu(tmpa)/20%CN Methyl violet: 10 mg·L−1 150W Xe 92.0% in 60 min [48][234]
22 MnCo2O4/g-C3N4 Nitrobenzene: 40 mg L−1 CMCN2/PMS system 96.7% in 240 min [61][244]
23 C3N4x/AgOy@Co1-xBi1-yO7 Oxytetracycline: 25 mL 25 mM 100 W tungsten bulb 93% in 160 min [57][12]
24 g-C3N4/WO3/WS2 Rhodamine B: 25 mg L−1 300 W Xe (>420 nm) 96.2% in 20 min [62][167]
25 Flower-like Bi12TiO20/g-C3N4 Rhodamine B: 20 mg·L−1 150 mW·cm−2 Xe (>420 nm) 100% in 30 min [63][245]
26 CdS/CQDs/g-C3N4 Rhodamine B: 10 mg·L−1 300 W Xe

(>420 nm)
100% in 20 min [64][246]
27 Ytterbium oxide-based GO/g-C3N4/Fe2O3 Rhodamine B: 10 mg·L−1 Light bulb 67.11% in 45 min [56][14]
28 Cerium-based GO/g-C3N4/Fe2O3 Rhodamine B: 10 mg·L−1 Light bulb 63.08% in 45 min [56][14]
29 Fish-scale g-C3N4/ZnIn2S4 Tetracycline: 10 mg·L−1 300 W Xe (>420 nm) 74% in 30 min [65][247]
31 Flower-like Co3O4/g-C3N4 Tetracycline: 15 mg·L−1 350 W Xe (>420 nm) 85.32% in 120 min [66][248]
31 10 wt% CuAl2O4/g-C3N4 Tetracycline hydrochloride: 100 mg·L−1 300 W Xe (>400 nm) 89.6% in 60 min [67][249]
32 CO-C3N4 Tetracycline hydrochloride: 10 mg·L−1 300 W Xe (>420 nm) 97.77% (PMS) in 40 min [68][250]
33 ZIF-67/g-C3N4 Venlafaxine: 10 mg·L−1 - 27.75% within 120 min [69][251]
34 ZIF-67/MIL-100(Fe)/g-C3N4 Venlafaxine: 10 mg·L−1 - 100% within 120 min [69][251]
35 ZIF-67/MOF-74(Ni)/g-C3N4 Venlafaxine: 10 mg·L−1 - 91.8% within 120 min [69][251]
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