CN117225444A - Photocatalytic material and preparation method and application thereof - Google Patents
Photocatalytic material and preparation method and application thereof Download PDFInfo
- Publication number
- CN117225444A CN117225444A CN202311094822.6A CN202311094822A CN117225444A CN 117225444 A CN117225444 A CN 117225444A CN 202311094822 A CN202311094822 A CN 202311094822A CN 117225444 A CN117225444 A CN 117225444A
- Authority
- CN
- China
- Prior art keywords
- photocatalytic material
- photocatalytic
- tri
- hydrochloride
- triaminobenzene
- Prior art date
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- 239000000463 material Substances 0.000 title claims abstract description 136
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 124
- 238000002360 preparation method Methods 0.000 title abstract description 10
- GSPBVFMIOSWQJB-UHFFFAOYSA-N benzene-1,3,5-triamine;trihydrochloride Chemical compound Cl.Cl.Cl.NC1=CC(N)=CC(N)=C1 GSPBVFMIOSWQJB-UHFFFAOYSA-N 0.000 claims abstract description 49
- 150000003839 salts Chemical class 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000001768 cations Chemical class 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 34
- 239000001257 hydrogen Substances 0.000 claims description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 27
- 239000004202 carbamide Substances 0.000 claims description 26
- 238000004519 manufacturing process Methods 0.000 claims description 25
- -1 poly-benzene nitride Chemical class 0.000 claims description 25
- 238000001354 calcination Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 12
- 239000005416 organic matter Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- BUKHSQBUKZIMLB-UHFFFAOYSA-L potassium;sodium;dichloride Chemical compound [Na+].[Cl-].[Cl-].[K+] BUKHSQBUKZIMLB-UHFFFAOYSA-L 0.000 claims description 9
- 238000006303 photolysis reaction Methods 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 6
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 claims description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 4
- 239000013067 intermediate product Substances 0.000 claims description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 4
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 2
- CIHHRNQZUFCQRG-UHFFFAOYSA-L [Li+].[K+].[Br-].[Br-] Chemical compound [Li+].[K+].[Br-].[Br-] CIHHRNQZUFCQRG-UHFFFAOYSA-L 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- HCQWRNRRURULEY-UHFFFAOYSA-L lithium;potassium;dichloride Chemical compound [Li+].[Cl-].[Cl-].[K+] HCQWRNRRURULEY-UHFFFAOYSA-L 0.000 claims description 2
- KXKFFNJPSQCIQR-UHFFFAOYSA-L magnesium sodium dichloride Chemical compound [Na+].[Mg+2].[Cl-].[Cl-] KXKFFNJPSQCIQR-UHFFFAOYSA-L 0.000 claims description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 22
- 230000031700 light absorption Effects 0.000 abstract description 16
- 230000007547 defect Effects 0.000 abstract description 12
- 230000009286 beneficial effect Effects 0.000 abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 11
- 239000000178 monomer Substances 0.000 abstract description 9
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 8
- 230000002708 enhancing effect Effects 0.000 abstract description 7
- 125000003118 aryl group Chemical group 0.000 abstract description 6
- 239000010439 graphite Substances 0.000 abstract description 4
- 229910002804 graphite Inorganic materials 0.000 abstract description 4
- 230000005012 migration Effects 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 4
- 239000000969 carrier Substances 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 22
- 239000000203 mixture Substances 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 238000000227 grinding Methods 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 11
- 239000011780 sodium chloride Substances 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 125000005843 halogen group Chemical group 0.000 description 10
- 125000003277 amino group Chemical group 0.000 description 9
- 230000008901 benefit Effects 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000003993 interaction Effects 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000006798 recombination Effects 0.000 description 6
- 238000005215 recombination Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- DKZXTOPFCDDGGX-UHFFFAOYSA-N tri-s-triazine Chemical compound C1=NC(N23)=NC=NC2=NC=NC3=N1 DKZXTOPFCDDGGX-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 238000013032 photocatalytic reaction Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 238000000103 photoluminescence spectrum Methods 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000012719 thermal polymerization Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 239000002262 Schiff base Substances 0.000 description 2
- 150000004753 Schiff bases Chemical class 0.000 description 2
- 150000001448 anilines Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 1
- 125000004398 2-methyl-2-butyl group Chemical group CC(C)(CC)* 0.000 description 1
- 125000004918 2-methyl-2-pentyl group Chemical group CC(C)(CCC)* 0.000 description 1
- 125000004922 2-methyl-3-pentyl group Chemical group CC(C)C(CC)* 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000004917 3-methyl-2-butyl group Chemical group CC(C(C)*)C 0.000 description 1
- 125000004919 3-methyl-2-pentyl group Chemical group CC(C(C)*)CC 0.000 description 1
- 125000004921 3-methyl-3-pentyl group Chemical group CC(CC)(CC)* 0.000 description 1
- 125000004920 4-methyl-2-pentyl group Chemical group CC(CC(C)*)C 0.000 description 1
- 125000006043 5-hexenyl group Chemical group 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- FRFILTWROYZEDS-UHFFFAOYSA-N N'-fluoroethane-1,2-diamine Chemical compound NCCNF FRFILTWROYZEDS-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- IWLAVQJQISQHPA-UHFFFAOYSA-L [F-].[Al+3].[F-].[Li+] Chemical compound [F-].[Al+3].[F-].[Li+] IWLAVQJQISQHPA-UHFFFAOYSA-L 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ILCQYORZHHFLNL-UHFFFAOYSA-N n-bromoaniline Chemical compound BrNC1=CC=CC=C1 ILCQYORZHHFLNL-UHFFFAOYSA-N 0.000 description 1
- KUDPGZONDFORKU-UHFFFAOYSA-N n-chloroaniline Chemical compound ClNC1=CC=CC=C1 KUDPGZONDFORKU-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- RRHNGIRRWDWWQQ-UHFFFAOYSA-N n-iodoaniline Chemical compound INC1=CC=CC=C1 RRHNGIRRWDWWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a photocatalytic material and a preparation method and application thereof. Relates to the technical field of photocatalysis. The photocatalytic material comprises the following raw materials of nitrogen-containing organic matters, molten salt containing metal cations and 1,3, 5-triaminobenzene tri-hydrochloride. According to the invention, an organic monomer 1,3, 5-triaminobenzene tri-hydrochloride (TAB) is introduced into a graphite phase nitrogen carbide structure, so that the 1.3.5-triaminobenzene tri-hydrochloride (TAB) is grafted on a carbon nitride network structure, and aromatic rings in-C [ identical to ] N, nitrogen defects and 1,3, 5-triaminobenzene tri-hydrochloride (TAB) structures formed in the network structure are beneficial to enhancing light absorption and separation and migration capacity of photogenerated carriers.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to a photocatalysis material and a preparation method and application thereof.
Background
Fujishima and Honda in TiO since 1972 2 Photocatalytic water splitting, which utilizes sunlight, water and semiconductors to produce hydrogen, has attracted considerable attention since the discovery of water photolysis on electrodes, because it is expected to be a sustainable and clean alternative to solving global energy and environmental problems. The key to realizing solar hydrogen production is to develop stable, efficient and inexpensive photocatalysts that can operate in the visible spectrum, with visible light accounting for about 50% of incident solar radiation on earth. In the pastHas been devoted to the development of visible light responsive photocatalysts, including modified TiO, for decades 2 And other metal oxides, metal (oxy) sulfides. There are also metal (oxy) nitrides. Meanwhile, other solar energy transducers have been studied, including conjugated polymers which are easy to process and fine tunable electronic structures, prepared using organic synthesis methods. However, most conventional conjugated semiconductors are chemically corroded by light irradiation in the presence of water and air. Graphitized carbon (g-C) 3 N 4 ) Polymers are the most stable allotrope of binary carbon nitride materials under ambient conditions, and due to their unique physicochemical properties, have been successfully used as metal-free visible light catalysts in 2009. Therefore, the photocatalyst is actively researched in the process of converting solar energy into chemical energy, such as hydrogen production by water, carbon dioxide conversion and organic selective synthesis.
However, pure graphitized carbon (g-C) 3 N 4 ) The polymers have only weak activity, in particular due to limited light absorption, rapid carrier recombination and low surface area. Most graphitized carbon polymers are still limited by moderate exciton dissociation, resulting in partial carrier recombination. This is because covalent graphitized carbon polymers, like most other polymer semiconductors, generally exhibit high exciton binding energies. In view of the structural features of g-C3N4, grafting of organic monomers in the CN network via an organic chemical route is indeed possible. The introduction of aromatic motifs in the CN network framework results in enhanced delocalization of pi electrons, thereby significantly improving light absorption and Photocatalytic Hydrogen Evolution (PHE). In addition, the use of molten salts as solvents and templates to accelerate the polymerization process and further tailor the structure and properties has been widely recognized as a viable method to synthesize materials with good properties, particularly metals and ionic compounds.
Therefore, a g-C with a defect structure and enhanced delocalization is synthesized by self-condensing a nitrogen-containing organic precursor and an aromatic motif-containing organic monomer by taking a salt melt as a high-temperature solvent 3 N 4 Is a novel method of (a). This work was to increase g-C 3 N 4 Provides a new idea for the photocatalytic activity of the polymer.
Disclosure of Invention
The first technical problem to be solved by the invention is as follows:
a photocatalytic material is provided.
The second technical problem to be solved by the invention is as follows:
a method for preparing the photocatalytic material is provided.
The third technical problem to be solved by the invention is:
the application of the photocatalytic material.
The invention also provides application of the photocatalytic material in hydrogen production reaction by photodecomposition of water under visible light.
The invention also provides application of the photocatalytic material in hydrogen production reaction by photodecomposition of water in dipotassium hydrogen phosphate environment.
In order to solve the first technical problem, the invention adopts the following technical scheme:
a photocatalytic material comprising the following raw materials:
nitrogen-containing organic matter, molten salt containing metal cations and 1,3, 5-triaminobenzene tri-hydrochloride.
According to the embodiments of the present invention, one of the technical solutions has at least one of the following advantages or beneficial effects:
in the graphite phase, nitrogen carbide (g-C) 3 N 4 ) The structure is introduced with organic monomer 1,3, 5-triaminobenzene tri-hydrochloride (TAB), so that the 1,3, 5-triaminobenzene tri-hydrochloride (TAB) is grafted on the carbon nitride network structure, and the covalent bond and electrostatic interaction formed in the grafting process can improve the transmission of electrons in the material. This means that the photoexcited electrons can propagate more efficiently in the material, thereby enhancing the efficiency of the photocatalytic reaction; the interaction formed in the grafting process is favorable for isolating electrons from holes, and the recombination between the electrons and the holes is reduced, so that the efficiency of photo-generated electron-hole separation is improved; the stable structure formed in the grafting process can prevent g-C 3 N 4 Structural destruction or dissolution in the photocatalytic reaction enhances the stability of the material.
In the network structure, the pi electron delocalization of the photocatalytic material can be enhanced by the-C.ident.N, nitrogen defects and aromatic rings in the 1,3, 5-triaminobenzene tri-hydrochloride (TAB) structure, which is beneficial to enhancing light absorption and rapid migration of photo-generated electrons. Since TAB contains an amino group, it can absorb light in a wider wavelength range, from ultraviolet to visible, which increases the absorption efficiency of the material for light.
The photocatalytic material can harvest more photons under the irradiation of visible light and inhibit the recombination of photon-generated carriers, thereby remarkably improving the H of the material under the irradiation of visible light and dipotassium hydrogen phosphate 2 Evolution efficiency.
In addition, not the conventional aminobenzene salts or certain organic monomers can achieve the same with g-C 3 N 4 The introduction of conventional aminobenzene salts or certain organic monomers may not enhance the light absorption capacity, electron transport efficiency and photogenerated electron-hole separation efficiency as effectively as TAB. In addition, the stability of the material may be reduced, affecting the photocatalytic performance. Therefore, in designing the photocatalytic material, a suitable organic monomer is selected for grafting to g-C 3 N 4 Structurally, it is important to consider the combination of structural compatibility and interaction effects to achieve optimal photocatalytic performance.
According to one embodiment of the present invention, the mass ratio of the 1,3, 5-triaminobenzene tri-hydrochloride (TAB) in the photocatalytic material is 0.2% to 0.3%.
The difference of the mass ratio of the 1,3, 5-triaminobenzene tri-hydrochloride (TAB) in the photocatalytic material can affect the structure of the photocatalytic material, thereby affecting the photocatalytic efficiency, hydrogen production yield and catalytic stability of the photocatalytic material.
According to one embodiment of the invention, the weight part ratio of the nitrogen-containing organic matter to the 1,3, 5-triaminobenzene tri-hydrochloride is 10000-12000:2-3. The ratio of the nitrogen-containing organic matter to 1,3, 5-triaminobenzene tri-hydrochloride (TAB) is adjusted to cause the 1,3, 5-triaminobenzene tri-hydrochloride (TAB) in the final polymer to change in a CN network structure, so that the photocatalytic material is obtained in different ratios under the NaCl-KCl fused salt environment.
According to one embodiment of the invention, the weight part ratio of the nitrogen-containing organic matter to the molten salt containing metal cations is 1000-1200:6-10.
According to one embodiment of the present invention, the nitrogen-containing organic matter comprises at least one of urea, formamide, acetamide, benzamide, acetonitrile, propionitrile, benzonitrile, pyrimidine, urea formaldehyde, cyanuric acid, poly-benzene nitride, pyrrolidone, and nitromethane.
According to one embodiment of the present invention, the metal cation-containing molten salt includes at least one of sodium chloride-potassium molten salt, potassium chloride-lithium molten salt, sodium fluoride-aluminum molten salt, lithium fluoride-aluminum fluoride, magnesium chloride-sodium chloride, and lithium bromide-potassium bromide.
According to one embodiment of the present invention, a photocatalytic material comprises the following raw materials:
urea (Urea), naCl-KCl molten salt and 1,3, 5-triaminobenzene tri-hydrochloride (TAB).
In the photocatalytic material, the 1,3, 5-triaminobenzene tri-hydrochloride (TAB) is grafted to graphite-phase carbon nitride.
According to an embodiment of the present invention, the photocatalytic material comprises the following structural formula:
wherein R is 1 、R 2 And R is 3 Independently selected from structures of formula II or formula III:
wherein R is 4 、R 5 And R is 6 Independently selected from amino, alkyl substituted amino, hydroxy substituted amino, halogen substituted amino, and the like;
wherein R is 7 And R is 8 Independently selected from formula I or formula II.
According to one embodiment of the present invention, the alkyl-substituted amino compound includes at least one of trimethylamine, isopropylamine, methylamine, ethylamine, tert-butylamine, octylamine, and cyclohexylamine. The alkyl substituent is introduced into the photocatalytic material, so that the photocatalytic stability and the pollution resistance of the material can be enhanced. The hydrophobic property can reduce the interaction between the material and polar substances such as water, and reduce the surface energy of the material, thereby being beneficial to improving the catalytic efficiency and prolonging the service life of the material.
According to one embodiment of the present invention, the hydroxy-substituted amino compound comprises at least one of an amino alcohol, an amino diol, an amino triol, an amino aldehyde, and an amino ketone. The hydroxyl substituted amino is introduced into the photocatalytic material, so that oxygen atoms and hydrogen atoms are introduced to form hydroxyl functional groups. The hydroxyl functional group has strong polarity in the photocatalytic material and is easy to generate hydrogen bond interaction with polar substances such as water. The hydroxyl substituent is introduced to enhance the interaction between the material and polar substances such as water and the like, and increase the active center of the catalytic reaction. In addition, the hydroxyl functional groups can also participate in some specific reactions to promote the catalytic activity and selectivity of the photocatalytic material.
According to one embodiment of the present invention, the halogen substituted amino compound includes at least one of trifluoromethane, fluoroethylenediamine, chloroaniline, bromoaniline, and iodoaniline. The halogen substituted amino is introduced into the photocatalytic material, so that halogen atoms are introduced, the halogen atoms have higher electronegativity and can influence the electronic structure of the material, the halogen substituent is introduced to adjust the energy band structure of the material, and additional energy levels are introduced to influence the transmission and separation of photogenerated electrons and holes. The regulation and control are beneficial to optimizing the photoelectron performance of the photocatalytic material, enhancing the light absorption capacity and the electron transmission efficiency, and further improving the catalytic performance and the photocatalytic activity.
According to one embodiment of the invention, the halogen in the halogen-substituted amino compound comprises F, cl, br and I.
According to one embodiment of the invention, fluorine is introduced into the photocatalytic material of the invention, and the high electronegativity of fluorine atoms enables the photocatalytic material with fluorine substituted amino groups to have higher catalytic activity and faster photo-generated electron transmission rate. The introduction of fluorine substituted amino groups can also improve the light absorption capacity of the composite material, thereby enhancing the photocatalytic activity.
According to one embodiment of the invention, chlorine is introduced into the photocatalytic material, the energy band structure of the photocatalytic material can be changed by introducing chlorine substituted amino, and the introduction of additional energy levels is beneficial to improving the transmission efficiency of photo-generated electrons and holes. In addition, the chlorine substituted amino groups can also increase the hydrophobicity of the composite material, thereby improving the stability and durability thereof.
According to one embodiment of the present invention, bromine is introduced into the photocatalytic material of the present invention, and the introduction of bromine substituted amino groups may cause structural changes on the surface of the material, increasing a certain number of active sites, thereby enhancing the catalytic performance of the photocatalytic material. In addition, bromine atoms have higher electronegativity, which is helpful for improving light absorption capacity.
According to one embodiment of the invention, iodine is introduced into the photocatalytic material, and the introduction of iodine substituted amino groups can change the surface structure of the material and increase active sites, so that the catalytic performance of the photocatalytic material is improved. Iodine atoms also have a high electronegativity, contributing to an improvement in light absorption capacity.
According to one embodiment of the invention, the electron density, the band structure and the surface properties of the photocatalytic material can be adjusted at the atomic level by introducing different halogen substituted amino groups, thereby achieving different advantages. These advantages include enhanced catalytic activity, improved light absorption, improved electron transport efficiency, and improved stability and durability of the material.
According to one embodiment of the present invention, the introduction of an amino substituent into the photocatalytic material of the present invention introduces additional nitrogen atoms into the photocatalytic material, the nitrogen atoms having lone pair electrons that enhance the absorption properties of the material. In addition, amino substituents can also form hydrogen bonds and other interactions, which can help to improve the stability and catalytic efficiency of the material, and in addition, amino substituents can increase the absorption properties of the material, making the photocatalytic material responsive to light over a wider range of wavelengths. In addition, by the special chemical property of the amino group, the amino group can also participate in the catalytic activity center in the reaction, and the light absorption and electron transmission efficiency of the photocatalytic material are enhanced.
According to an embodiment of the invention, when R 1 And R is 2 At least one of the structures shown in the formula III, namely when the photocatalytic material contains a carbon-nitrogen triple bond, has the following advantages: the formation of the carbon-nitrogen triple bond increases the conductivity and electron delocalization of the material, is beneficial to the rapid transmission and separation of photogenerated electrons in the material, reduces the recombination of electrons and holes, and improves the efficiency of photocatalytic reaction; due to the introduction of carbon-nitrogen triple bonds, active sites on the surface of the photocatalytic material are increased, and the active sites can be used as catalytic centers of photocatalytic reaction, so that the catalytic activity and efficiency of the photocatalytic material are improved; in addition, the formation of the carbon-nitrogen triple bond introduces a carbon nitride-containing structure, and the structure has good light absorption performance and can effectively absorb energy of visible light and ultraviolet light.
In order to solve the second technical problem, the invention adopts the following technical scheme:
a method of preparing the photocatalytic material comprising the steps of:
s1, mixing a nitrogen-containing organic matter and 1,3, 5-triaminobenzene tri-hydrochloride, and calcining to obtain an intermediate product;
s2, mixing the intermediate product with molten salt containing metal cations under protective atmosphere, and calcining to obtain the photocatalytic material.
According to the embodiments of the present invention, one of the technical solutions has at least one of the following advantages or beneficial effects:
in the preparation method, after heating the nitrogen-containing organic matter, graphite-phase carbon nitride can be obtained through polymerization reaction, wherein the graphite-phase carbon nitride has a structural unit of tris-s-triazine; and the graphite phase carbon nitride and 1,3, 5-triaminobenzene tri-hydrochloride (TAB) are subjected to Schiff base reaction to obtain the 1,3, 5-triaminobenzene tri-hydrochloride (TAB) which is grafted on the photocatalytic material of the tri-s-triazine, so that the photocatalytic material with enhanced delocalization and containing-C.ident.N and nitrogen defects is obtained under the fused salt calcination environment of the second step.
The preparation of the photocatalytic material by the method can improve g-C 3 N 4 The photocatalytic performance of (graphite phase carbon nitride) widens the photoresponse range of the material and improves the electron hole separation rate; the method utilizes high-temperature two-step thermal polymerization to prepare the photocatalytic material of the visible light response 1,3, 5-triaminobenzene tri-hydrochloride (TAB) grafted CN network structure, and has the advantages of simple operation, high reaction efficiency, good preparation material performance and the like.
According to one embodiment of the invention, the polymerization reaction is a thermal polycondensation process. The thermal polycondensation method is to prepare g-C by pyrolysis treatment of nitrogen-rich precursor 3 N 4 . The method has the characteristics of cheap raw materials, simple preparation process and good product crystal form.
According to one embodiment of the invention, the method further comprises the operation of grinding after cooling the first step reactant. The ground reactant is subjected to the second-step thermal polymerization, and the reaction is more complete.
According to one embodiment of the present invention, the ratio of the calcining temperature in the step S1 to the calcining temperature in the step S2 is 500 to 550:600-650. The two different reaction stages employ different temperatures, the mass ratio of Urea (Urea) to different 1,3, 5-triaminobenzenetriamine hydrochloride (TAB) affecting the catalytic performance of the reaction product of the first step.
According to one embodiment of the invention, when the metal cation-containing molten salt is a mixture of NaCl and KCl, the mass ratio of NaCl to KCl is 4-6:1-3.
According to an embodiment of the present invention, in step S2, the method further comprises the steps of: washing the calcined product with hot water, and drying.
According to one embodiment of the present invention, the hot water washing is followed by a drying process, comprising the steps of: molten salt is washed by hot water filtration and then dried in a vacuum oven for 2-3 hours.
In another aspect, the invention also relates to application of the photocatalytic material in a hydrogen production reaction by photodecomposition of water under visible light. Comprising a photocatalytic material as described in the above embodiment of aspect 1. The application adopts all the technical schemes of the photocatalytic material, so that the photocatalytic material has at least all the beneficial effects brought by the technical schemes of the embodiment.
In another aspect, the invention also relates to application of the photocatalytic material in hydrogen production reaction by photodecomposition of water in dipotassium hydrogen phosphate environment. Comprising a photocatalytic material as described in the above embodiment of aspect 1. The application adopts all the technical schemes of the photocatalytic material, so that the photocatalytic material has at least all the beneficial effects brought by the technical schemes of the embodiment.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a process step diagram for preparing the photocatalytic material according to example 1.
FIG. 2 is a spectrum showing the diffuse reflection of ultraviolet light in the materials obtained in examples 1 to 3 and comparative examples 1 to 3.
FIG. 3 is a photoluminescence spectrum of the materials obtained in examples 1 to 3 and comparative examples 1 to 3.
FIG. 4 is a graph showing the photocatalytic hydrogen production rate of the materials obtained in examples 1 to 3 and comparative examples 1 to 3.
FIG. 5 is a graph showing the photocatalytic stability test of the material obtained in example 2.
FIG. 6 is an X-ray diffraction pattern of the materials obtained in examples 1-3 and comparative examples 1-3.
Detailed Description
In the description of the present invention, the description of first, second, etc. is for the purpose of distinguishing between technical features only and should not be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated.
In the description of the present invention, it should be understood that references to orientation descriptions, such as directions or positional relationships indicated above, below, etc., are based on the orientation or positional relationships shown in the embodiments, are merely for convenience of description of the present invention and to simplify the description, and do not indicate or imply that the apparatus or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus should not be construed as limiting the present invention.
The words "preferably," "more preferably," and the like in the present invention refer to embodiments of the invention that may provide certain benefits in some instances. However, other embodiments may be preferred under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values for the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The reagents, methods and apparatus employed in the present invention, unless otherwise specified, are all conventional in the art.
Unless otherwise indicated or contradicted, terms or phrases used herein have the following meanings:
in an embodiment, the term "alkyl" refers to a saturated hydrocarbon containing primary (positive) carbon atoms, or secondary carbon atoms, or tertiary carbon atoms, or quaternary carbon atoms, or a combination thereof. Phrases containing this term, e.g., "C 1-8 Alkyl "refers to an alkyl group containing 1 to 8 carbon atoms. Suitable examples include, but are not limited to: methyl (Me, -CH) 3 ) Ethyl (Et, -CH) 2 CH 3 ) 1-propyl (n-Pr, n-propyl, -CH 2 CH 2 CH), 2-propyl (i-Pr, i-propyl, -CH (CH) 3 ) 2 ) 1-butyl (n-Bu, n-butyl, -CH) 2 CH 2 CH 2 CH 3 ) 2-methyl-1-propyl (i-Bu, i-butyl, -CH) 2 CH(CH 3 ) 2 ) 2-butyl (s-Bu, s-butyl, -CH (CH) 3 )CH 2 CH 3 ) 2-methyl-2-propyl (t-Bu, t-butyl, -C (CH) 3 ) 3), 1-pentyl (n-pentyl, -CH 2 CH 2 CH 2 CH 2 CH 3 ) 2-pentyl (-CH (CH) 3 )CH 2 CH 2 CH 3 ) 3-pentyl (-CH (CH) 2 CH 3 ) 2 ) 2-methyl-2-butyl (-C (CH) 3 ) 2 CH 2 CH 3 ) 3-methyl-2-butyl (-CH (CH) 3 )CH(CH 3 ) 2 ) 3-methyl-1-butyl (-CH) 2 CH 2 CH(CH 3 ) 2 ) 2-methyl-1-butyl (-CH) 2 CH(CH 3 )CH 2 CH 3 ) 1-hexyl (-CH) 2 CH 2 CH 2 CH 2 CH 2 CH 3 ) 2-hexyl (-CH (CH) 3 )CH 2 CH 2 CH 2 CH 3 ) 3-hexyl (-CH (CH) 2 CH 3 )(CH 2 CH 2 CH 3 ) 2-methyl-2-pentyl (-C (CH) 3 ) 2 CH 2 CH 2 CH 3 ) 3-methyl-2-pentyl (-CH (CH) 3 )CH(CH 3 )CH 2 CH 3 )、4-methyl-2-pentyl (-CH (CH) 3 )CH 2 CH(CH 3 ) 2 ) 3-methyl-3-pentyl (-C (CH) 3 )(CH 2 CH 3 ) 2 ) 2-methyl-3-pentyl (-CH (CH) 2 CH 3 )CH(CH 3 ) 2 ) 2, 3-dimethyl-2-butyl (-C (CH) 3 ) 2 CH(CH 3 ) 2 ) 3, 3-dimethyl-2-butyl (-CH (CH) 3 )C(CH 3 ) 3 and octyl (- (CH) 2 ) 7 CH 3 )。
In the examples, "C 1～10 Alkyl "refers to an alkyl group having 1 to 10 carbon atoms and is meant to include both branched and straight chain saturated aliphatic hydrocarbon groups having the indicated number of carbon atoms. For example, C 1 ～ 10 As in "C 1 ～ 10 Alkyl "is defined to include groups having 1, 2,3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms in a straight or branched chain structure. For example, "C 1 ～ 10 The alkyl group "specifically includes methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and the like.
In the examples, "C 1～4 The alkyl group "means an alkyl group having 1 to 4 carbon atoms, and includes, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and the like.
In the examples, "C 1 ～ 10 Alkoxy "means an alkyl group as defined above attached through an oxygen atom, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, and the like. Similarly, "C 1 ～ 10 Haloalkyl "refers to halogen substituted alkyl as defined above.
In the examples, "alkenyl" is meant to include a radical having at least one unsaturated site, i.e., carbon-carbon sp 2 A hydrocarbon of a normal carbon atom, a secondary carbon atom, a tertiary carbon atom or a cyclic carbon atom of the double bond. Phrases containing this term, e.g., "C 2-8 Alkenyl "refers to alkenyl groups containing 2 to 8 carbon atoms. Suitable examples include, but are not limited to: vinyl (-ch=ch) 2 ) Propenyl (-CH) 2 CH＝CH 2 ) Cyclopentenyl (-C) 5 H 7 ) And 5-hexenyl (-CH) 2 CH 2 CH 2 CH 2 CH＝CH 2 )。
In embodiments, halogen "or" halo "refers to F, cl, br or I.
In embodiments, "halo substituted" means that an optional amount of H at any optional position on the corresponding group is substituted with halo, e.g., fluoromethyl, including monofluoromethyl, difluoromethyl, trifluoromethyl.
Example 1
The preparation method of the photocatalytic material is shown in fig. 1, and specifically comprises the following steps:
(1) Weighing 20g of Urea (Urea) and 4mg of 1,3, 5-triaminobenzene tri-hydrochloride (TAB), uniformly mixing and grinding, then transferring the mixture into a 100mL alumina crucible with a cover, and calcining for 2 hours at 500 ℃ in a muffle furnace;
(2) The solid powder obtained was ground and weighed 2g and 6.0g of metal salts (4.28 g NaCl and 1.72g KCl) were ground for 20min, then calcined in a nitrogen-vented tube furnace at 600℃for 2h;
(3) Naturally cooling to room temperature, thoroughly cleaning the mixture with deionized water, and drying in a vacuum oven.
The photocatalytic material is prepared through the steps, and a sample is named UCN-4TAB-NaK.
As shown in FIG. 1, wherein Urea (Urea) can be obtained as g-C by polymerization 3 N 4 ，g-C 3 N 4 Having structural units of tris-s-triazine.
Wherein, urea (Urea) and 1,3, 5-triaminobenzene tri-hydrochloride (TAB) are subjected to Schiff base reaction to obtain 1,3, 5-triaminobenzene tri-hydrochloride (TAB) which is grafted on a structural unit of tri-s-triazine, the unit is a photocatalytic material, the photocatalytic material can further repeat the reaction to obtain a novel structural unit of 1,3, 5-triaminobenzene tri-hydrochloride (TAB) which is grafted on the tri-s-triazine, and the novel photocatalytic material is obtained.
When other substances with a tri-s-triazine structure are further added, the photocatalytic material can further repeat the reaction to obtain a new 1,3, 5-triaminobenzene tri-hydrochloride (TAB) grafted on the structural unit of the tri-s-triazine, and thus the novel photocatalytic material is obtained.
When the material is ground and calcined with 6.0g of metal salt (4.28 g of NaCl and 1.72g of KCl) in the second step, K/Na ions are introduced into the material as a charge compensator to balance NH in molten salt thermal polymerization 3 The grafting treatment of eutectic NaCl-KCl salts and TAB results in nitrogen defects and-C.ident.N. Finally, the high-performance photocatalytic material with enhanced delocalization and containing-C.ident.N and nitrogen defects can be obtained.
Example 2
A method of preparing a photocatalytic material comprising the steps of:
(1) Weighing 20g of Urea (Urea) and 5mg of 1,3, 5-triaminobenzene tri-hydrochloride (TAB), uniformly mixing and grinding, then transferring the mixture into a 100mL alumina crucible with a cover, and calcining for 2 hours at 500 ℃ in a muffle furnace;
(2) The solid powder obtained was ground and weighed 2g and 6.0g of metal salts (4.28 g NaCl and 1.72g KCl) were ground for 20min, then calcined in a nitrogen-vented tube furnace at 600℃for 2h;
(3) Naturally cooling to room temperature, thoroughly cleaning the mixture with deionized water, and drying in a vacuum oven.
The photocatalytic material is prepared through the steps, and a sample is named UCN-5TAB-NaK.
Compared with example 1, the difference was that only 1,3, 5-triaminobenzene tri-hydrochloride (TAB) was added in an amount of 5mg, and the prepared sample was named UCN-5TAB-NaK.
Example 3
A method of preparing a photocatalytic material comprising the steps of:
(1) Weighing 20g of Urea (Urea) and 6mg of 1,3, 5-triaminobenzene tri-hydrochloride (TAB), uniformly mixing and grinding, then transferring the mixture into a 100mL alumina crucible with a cover, and calcining for 2 hours at 500 ℃ in a muffle furnace;
(2) The solid powder obtained was ground and weighed 2g and 6.0g of metal salts (4.28 g NaCl and 1.72g KCl) were ground for 20min, then calcined in a nitrogen-vented tube furnace at 600℃for 2h;
(3) Naturally cooling to room temperature, thoroughly cleaning the mixture with deionized water, and drying in a vacuum oven.
The photocatalytic material is prepared through the steps, and a sample is named UCN-6TAB-NaK.
Compared with example 1, the difference was that only 1,3, 5-triaminobenzene tri-hydrochloride (TAB) was added in an amount of 6mg, and the prepared sample was named UCN-6TAB-NaK.
Examples 1-3 differ only in the amount of 1,3, 5-Triaminobenzenetrihydrochloride (TAB) added.
The invention grafts 1,3, 5-triaminobenzene tri-hydrochloride (TAB) into g-C 3 N 4 The photocatalytic material of the present invention can be obtained by a network structure and performing a second calcination treatment in a molten salt environment.
The obtained material has different ratios of 1,3, 5-triaminobenzene tri-hydrochloride (TAB) in the composite material of the CN network due to different addition amounts of the 1,3, 5-triaminobenzene tri-hydrochloride (TAB), so that certain differences exist in chemical properties and catalytic efficiency.
By adjusting the ratio of Urea (Urea) to 1,3, 5-triaminobenzene tri-hydrochloride (TAB), the 1,3, 5-triaminobenzene tri-hydrochloride (TAB) in the final polymer is caused to be at g-C 3 N 4 The network structure is changed, and the photocatalytic material with different proportions is obtained.
Example 4
A method of preparing a photocatalytic material comprising the steps of:
(1) Weighing 22.4g of urea formaldehyde and 4mg of 1,3, 5-triaminobenzene tri-hydrochloride (TAB), uniformly mixing and grinding, then transferring the mixture into a 100mL aluminum oxide crucible with a cover, and calcining for 2 hours at 500 ℃ in a muffle furnace;
(2) The solid powder obtained was ground and weighed 2g and 6.0g of metal salts (4.28 g NaCl and 1.72g KCl) were ground for 20min, then calcined in a nitrogen-vented tube furnace at 600℃for 2h;
(3) Naturally cooling to room temperature, thoroughly cleaning the mixture with deionized water, and drying in a vacuum oven.
In comparison with example 1, the only difference is that the nitrogen-containing organic matter is urea formaldehyde.
Example 5
A method of preparing a photocatalytic material comprising the steps of:
(1) 15.8g of cyanuric acid and 4mg of 1,3, 5-triaminobenzene tri-hydrochloride (TAB) are weighed, mixed and ground uniformly, and then the mixture is transferred into a 100mL alumina crucible with a cover and calcined in a muffle furnace at 500 ℃ for 2h;
(2) The solid powder obtained was ground and weighed 2g and 6.0g of metal salts (4.28 g NaCl and 1.72g KCl) were ground for 20min, then calcined in a nitrogen-vented tube furnace at 600℃for 2h;
(3) Naturally cooling to room temperature, thoroughly cleaning the mixture with deionized water, and drying in a vacuum oven.
In comparison with example 1, the only difference is that the nitrogen-containing organic is cyanuric acid.
Example 6
A method of preparing a photocatalytic material comprising the steps of:
(1) Weighing 20g of Urea (Urea) and 4mg of 1,3, 5-triaminobenzene tri-hydrochloride (TAB), uniformly mixing and grinding, then transferring the mixture into a 100mL alumina crucible with a cover, and calcining for 2 hours at 500 ℃ in a muffle furnace;
(2) The solid powder obtained was ground and weighed 2g and 6.0g of metal salts (4.28 g LiCl and 1.72g KCl) for 20min, then calcined in a nitrogen-vented tube furnace at 600 ℃ for 2h;
(3) Naturally cooling to room temperature, thoroughly cleaning the mixture with deionized water, and drying in a vacuum oven.
Compared to example 1, the only difference is the metal salts LiCl and KCl.
Comparative example 1
Pure phase g-C 3 N 4 The preparation method of the photocatalyst comprises the following steps:
weighing 20g of Urea (Urea), grinding uniformly, placing in a 100ml aluminum oxide crucible with a cover, placing the crucible in a muffle furnace, gradually heating to 500 ℃ at a heating rate of 10 ℃/min, and heating at a constant temperature of 600 ℃ for 2 hours in a tubular furnace; naturally cooling to room temperature, and grinding the obtained sample again sufficiently.
In comparison with example 2, except that 1,3, 5-Triaminobenzenetrihydrochloride (TAB) and 6.0g metal salt (4.28 g NaCl and 1.72g KCl) were not added, the prepared sample was named UCN.
Comparative example 2
A method of preparing a photocatalytic material comprising the steps of:
(1) Weighing 20g of Urea (Urea) and 5mg of 1,3, 5-triaminobenzene tri-hydrochloride (TAB), uniformly mixing and grinding, then transferring the mixture into a 100mL alumina crucible with a cover, and calcining for 2 hours at 500 ℃ in a muffle furnace;
(2) Grinding the obtained solid powder for 20min, and calcining for 2h at 600 ℃ in a tube furnace filled with nitrogen;
(3) Naturally cooling to room temperature, grinding and collecting.
The photocatalytic material is prepared through the steps, and a sample is named UCN-5TAB.
In comparison with example 2, the only difference was that 6.0g of metal salt (4.28 g of NaCl and 1.72g of KCl) was not added and that the drying process was water-washed, and the prepared sample was designated UCN-5TAB.
Comparative example 3
A method of preparing a photocatalytic material comprising the steps of:
(1) Weighing 20g of Urea (Urea), grinding uniformly, transferring to a 100mL aluminum oxide crucible with a cover, and calcining for 2 hours at 500 ℃ in a muffle furnace;
(2) The solid powder obtained was ground and weighed 2g and 6.0g of metal salts (4.28 g NaCl and 1.72g KCl) were ground for 20min, then calcined in a nitrogen-vented tube furnace at 600℃for 2h;
(3) Naturally cooling to room temperature, thoroughly cleaning the mixture with deionized water, and drying in a vacuum oven.
The photocatalytic material is prepared through the steps, and a sample is named UCN-NaK.
In comparison with example 2, the sample prepared was named UCN-NaK, except that 5mg of 1,3, 5-Triaminobenzenetrihydrochloride (TAB) was not added.
Performance test:
test example 1:
ultraviolet visible diffuse reflection experiment:
the photocatalytic materials obtained in examples 1 to 3 and the photocatalytic materials obtained in comparative examples 1 to 3 were subjected to ultraviolet-visible diffuse reflection spectra, and the test is shown in FIG. 2.
Wherein, the used instrument of ultraviolet visible diffuse reflection spectrum test is: hitachi U-3010UV-vis spectrometer using BaSO 4 As a reference.
As can be seen from fig. 2, the maximum absorption observed for the samples at 350-400nm is due to pi-pi transitions of the conjugated ring system. All UCN-NaK and UCN-xTAB-NaK show significant enhancement of visible light absorption in the range of 300-460nm compared to UCN, which can be attributed to the introduction of nitrogen defects and cyano groups. Since both coordinating nitrogen atoms are replaced by CH groups during copolymerization, the absorption edge extends to longer wavelengths. Thus, as the TAB loading increases, the light absorption of UCN-xTAB-NaK between 460nm and 700nm gradually increases. The enhanced light absorption of the sample indicates electron and hole stabilization of the excited state, indicating that photochemistry may be utilized even at long wavelengths.
Test example 2:
photoluminescence spectrum test:
wherein, the specific experimental conditions are as follows: FLS-980 fluorescence spectrometer was used at room temperature.
Photoluminescence spectra of the samples obtained in examples 1 to 3 and comparative examples 1 to 3 are shown in fig. 3.
As can be seen from fig. 3, with the introduction of TAB or NaCl-KCl molten salt in the CN network, PL intensity was significantly reduced due to enhanced delocalization in UCN-5TAB and inclusion of formation defects (e.g., N defects and cyano groups) in UCN-NaK. The photoluminescent intensity of UCN-xba-NaK was further reduced, suggesting a good synergistic effect between delocalization and defect-containing. The formed defect-containing and enhanced delocalization can accelerate dissociation of singlet excitons, thereby promoting effective separation of carriers.
In addition, a progressive red shift of the emission peak of UCN-xTAB-NaK can be observed compared to UCN, highlighting the improved stability of photogenerated electrons and holes. With the addition of the 1,3, 5-triaminobenzene tri-hydrochloride (TAB), the composite material obtained after grafting the 1,3, 5-triaminobenzene tri-hydrochloride (TAB) on the CN network structure can effectively promote the separation of the photo-generated electrons and the photo-generated holes of the sample. This is due to the enhanced delocalization of pi electrons and the rapid migration of photogenerated electrons as the organic monomer 1,3, 5-triaminobenzene tri-hydrochloride (TAB) is grafted onto the CN network. Thereby inhibiting the rapid recombination of photo-generated holes and photo-generated electrons and promoting the photocatalytic hydrogen production activity of the catalyst.
Test example 3:
photocatalytic hydrogen production rate experiments:
the specific experimental conditions and methods are as follows: labsora-6A photocatalytic on-line analysis System, available from Beijing Porphy technologies Co.
Wherein, specific reaction solution: 50mg of photocatalytic material was added to 100mL of an aqueous solution containing 10mL of the sacrificial agent triethanolamine, and 5wt% Pt was used as a promoter, light source PLS-SxE 5/5UV, light intensity: 100mW/cm 2 ，λ>420nm。
The photocatalytic materials obtained in examples 1 to 3 and the photocatalytic materials obtained in comparative examples 1 to 3 were tested for photocatalytic hydrogen production rate by the above experimental conditions and methods, and the results are shown in fig. 4. Fig. 4 (a) is a graph showing the hydrogen production rate of the products of examples 1 to 3 and comparative examples 1 to 3, and fig. 4 (b) is a graph showing the hydrogen production rate of example 2 at different wavelengths.
As can be seen from FIG. 4, almost all of the 1,3, 5-triaminobenzene tri-hydrochloride (TAB) grafted g-C under NaCl-KCl molten salt compared with the original UCN sample (material prepared in comparative example) 3 N 4 Composite material: UCN-xTAB-NaK has obvious improvement of photocatalytic hydrogen production performance.
The hydrogen production rate of the sample UCN prepared in comparative example 1 is 78 mu mol h under the condition that the wavelength is more than or equal to 420nm -1 Significantly lower than 394. Mu. Mol h of UCN-5TAB-NaK prepared in sample example 2 -1 ；
The hydrogen production rate of UCN-4TAB-NaK prepared in example 1 was 163. Mu. Mol h -1 Lower than UCN-5TAB-NaK prepared in example 2;
the UCN-6TAB-NaK prepared in example 3 had a hydrogen production rate of 93. Mu. Mol h -1 Lower than implementation ofUCN-5TAB-NaK prepared in example 2;
more importantly, unlike the rapid decay of UCN-NaK, UCN-xbab-NaK retains good activity even at 500 and 550nm due to the introduction of TAB accompanied by pi→pi electron transitions and enhanced delocalization. The synergistic effect derived from the introduction of TAB and NaCl-KCl molten salt treatment can effectively promote the activity of Photocatalytic Hydrogen Evolution (PHE) in the long wavelength range.
UCN-5TAB-NaK prepared in example 2 in the presence of dipotassium hydrogen phosphate (K 2 HPO 4 ) Has very good performance in hydrogen production under the environment. Specifically, when dipotassium hydrogen phosphate (K) 2 HPO 4 ) The hydrogen production efficiency of UCN-5TAB-NaK under the irradiation of simulated sunlight and visible light is 2352 mu mol h under the condition of simulated sunlight (AM1.5G) -1 1047. Mu. Mol h at 420nm -1 528 mu mol h at 450nm -1 29 mu mol h at 500nm -1 And 9. Mu. Mol h at 550nm -1 Respectively is K-free 2 HPO 4 5.9 and 2.6 times.
In summary, the sample UCN-5TAB-NaK obtained by grafting a proper amount of 1,3, 5-triaminobenzene tri-hydrochloride (TAB) with a CN network structure under the assistance of NaCl-KCl molten salt has the highest photocatalytic hydrogen production performance, namely, the photocatalytic hydrogen production rate of the photocatalytic material prepared in the embodiment 2 is optimal.
With further increase of the amount of 1,3, 5-triaminobenzene tri-hydrochloride (TAB), the hydrogen production performance of the prepared photocatalytic material sample gradually decreases, which may be caused by excessive doping, and damage some properties of the semiconductor to affect the photocatalytic performance of the material.
Test example 4:
photocatalytic stability experiments:
the photocatalytic stability test of the sample UCN-5TAB-NaK obtained in example 2 is shown in FIG. 5.
As can be seen from fig. 5, after testing for 5 cycles (evacuating and discharging generated hydrogen every 4 hours, calculating one cycle) with continuous illumination for 20 hours, the hydrogen generating activity of the sample UCN-5TAB-NaK is basically not attenuated, which proves that the catalyst has good stability and good application prospect in practical application.
Test example 5:
x-ray diffraction experiment:
x-ray diffraction patterns 6 of the samples UCN, UCN-5TAB, UCN-NaK and UCN-5TAB-NaK obtained in comparative examples 1-3 and examples 1-3 are shown.
As can be seen from fig. 6, all of the above samples showed typical characteristic peaks of two graphite-like carbon nitrides associated with (100) and (002) crystal planes, corresponding to the crystal plane stack and interlayer stack structure of heptazine, respectively.
Compared with the original UCN, UCN-5mg material doped with the tri-hydrochloride, the diffraction peaks at (100) and (002) are slightly widened, which is attributed to the influence on the crystallinity of the material after the tri-hydrochloride monomer is doped.
After the NaK mixed salt treatment, the (100) face of the material is shifted by 5.9 degrees at a small angle, which can be attributed to the fact that metal ions enter a CN network so that the in-plane spacing of the material is increased and the in-plane stacking distance is enlarged. Wherein the (002) peak position is shifted to a small angle by 0.57 °, indicating that the inter-layer unit distance of the triazine structure is increased, which is attributable to HCl and NH generated in the reaction system 4 Cl and other gases expand the interlayer stacking distance of the material. Since the hot water washing treatment was performed, no diffraction peak of NaK occurred.
Based on these characterization results, the aromatic ring structure can be grafted into the CN framework by adding TAB. The use of eutectic NaCl-KCl salts leads to nitrogen defects and-C.ident.N. In addition, aromatic rings in C.ident.N and 1,3, 5-triaminobenzene tri-hydrochloride (TAB) can enhance pi electron delocalization, thereby being beneficial to enhancing light absorption and fast migration of photo-generated electrons and promoting the photocatalytic hydrogen production activity of the catalyst.
The foregoing is merely exemplary embodiments of the present invention and are not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention or direct or indirect application in the relevant art are intended to be included in the scope of the present invention.
Claims (10)
1. A photocatalytic material, characterized by: the photocatalytic material comprises the following raw materials:
nitrogen-containing organic matter, molten salt containing metal cations and 1,3, 5-triaminobenzene tri-hydrochloride.
2. A photocatalytic material according to claim 1, characterized in that: the weight ratio of the nitrogen-containing organic matter to the 1,3, 5-triaminobenzene tri-hydrochloride is 10000-12000:2-3.
3. A photocatalytic material according to claim 1, characterized in that: the weight ratio of the nitrogen-containing organic matters to the molten salt containing the metal cations is 1000-1200:2-3.
4. A photocatalytic material according to claim 1, characterized in that: the nitrogen-containing organic matter comprises at least one of urea, formamide, acetamide, benzamide, acetonitrile, propionitrile, benzonitrile, pyrimidine, urea formaldehyde, cyanuric acid, poly-benzene nitride, pyrrolidone and nitromethane.
5. A photocatalytic material according to claim 1, characterized in that: the metal cation-containing molten salt includes at least one of sodium chloride-potassium molten salt, potassium chloride-lithium molten salt, sodium fluoride-aluminum molten salt, lithium fluoride-aluminum fluoride-lithium fluoride, magnesium chloride-sodium chloride, and lithium bromide-potassium bromide.
6. A method of preparing a photocatalytic material according to any one of claims 1 to 5, characterized in that: the method comprises the following steps:
s1, mixing a nitrogen-containing organic matter and 1,3, 5-triaminobenzene tri-hydrochloride, and calcining to obtain an intermediate product;
s2, mixing the intermediate product with molten salt containing metal cations under protective atmosphere, and calcining to obtain the photocatalytic material.
7. The method according to claim 6, wherein: the ratio of the calcining temperature in the step S1 to the calcining temperature in the step S2 is 500-550:600-650.
8. The method according to claim 6, wherein: in step S2, the method further includes the following steps: washing the calcined product with hot water, and drying.
9. The method according to claim 6, wherein: the hot water washing is followed by drying treatment, which comprises the following steps: molten salt is washed by hot water filtration and then dried in a vacuum oven for 2-3 hours.
10. Use of a photocatalytic material according to any one of claims 1 to 5 for the photocatalytic hydrogen production reaction by photodecomposition of water under visible light or for the photocatalytic hydrogen production reaction by photodecomposition of water under dipotassium hydrogen phosphate.
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