Theoretical Studies on the Phenoxyalkanoic Herbicides Adsorption on Kaolinite Surface†

doi:10.7503/cjcu20150078

Abstract

Abstract:

Octahedral(Al—O) surface model Al₁₃O₄₈H₅₇ and tetrahedral(Si—O) surface model Si₁₃O₃₇H₂₂ were constructed, and the B3LYP/6-31G(d,p) level was used to research the interaction and properties including optimal structures, structural parameters, adsorption energies, natural bond orbit(NBO) charge distributions, between Kaolinite and 2,4-dichlorophenoxyacetic acid(2,4-D), 2,4-dichlorophenoxypropanoic acid(2,4-DP), 2,4-dichlorophenoxybutyric acid(2,4-DB), 2-methyl-4-chlorophenoxyacetic acid(MCPA), 2-methyl-4-chlorophenoxypropanoic acid(MCPP), 2-methyl-4-chlorophenoxybutyric acid(MCPB). Simultaneously, adsorption of MCPP on Kaolinite surface was stronger than that of MCPA. Combined with conclusion of experiment that 2,4-D has higher adsorption than MCPA, we can infer that 2,4-D and MCPA tend to be adsorbed on tetrahedral surface. Therefore, interaction of herbicides on Kaolinite should be taken full account of to ensure the feasibility of leaching in removing herbiside residues in the process of fertilization.

Key words: Phenoxyalkanoic herbicide, Residue, Al—O Octahedral surface, Si—O Tetrahedral surface

CLC Number:

O641

TrendMD:

WANG Liang, ZHANG Chao, ZHONG Mingjing, QIAN Ping. Theoretical Studies on the Phenoxyalkanoic Herbicides Adsorption on Kaolinite Surface^†[J]. Chem. J. Chinese Universities, 2015, 36(7): 1358.

Figures/Tables 9

Fig.1 Pesticide general structure

Fig.2 Kaolinite octahedral surface model(A) and tetrahedral surface model(B)

Fig.3 Optimal structures of 2,4-D, 2,4-DP, 2,4-DB, MCPA, MCPP and MCPB

Fig.4 Optimal structures of pesticides on octahedral surface

Table 1 Hydrogen bond lengths(d) of various low energy structures for phenoxyalkanoic herbicides on Kaolinite

System	E_A(BSSE)/ (kJ·mol^-1)	$n Hb a$	d(H…O)/nm
			C—H…O				O—H…O
			H1^b	H2^b	H3^b	H4^b		H1^b	H2^b	H3^b	H4^b
K(o)-2,4-D1	-35.36	3	0.28						0.18	0.18
K(o)-2,4-D2	-22.58	3						0.21	0.19	0.22
K(o)-2,4-DP1	-4.48	4			0.22	0.24		0.24	0.21
K(o)-2,4-DB1	-66.99	4	0.28						0.20	0.21	0.15
K(o)-2,4-DB2	-58.04	4						0.24	0.20	0.25	0.16
K(o)-MCPA1	-43.83	4	0.27						0.21	0.23	0.17
K(o)-MCPA2	-42.15	4	0.27						0.21	0.22	0.18
K(o)-MCPP1	-60.82	4		0.26				0.20		0.16	0.26
K(o)-MCPP2	-31.60	4						0.20	0.23	0.17	0.19
K(o)-MCPP3	-17.05	3	0.26						0.21	0.20
K(o)-MCPB1	-65.96	4	0.23	0.26	0.26						0.20
K(o)-MCPB2	-7.84	3		0.24	0.25			0.21
K(t)-2,4-D1	-33.62	3	0.27	0.27						0.22
K(t)-2,4-D2	-29.83	3	0.28	0.27						0.21
K(t)-2,4-DP1	-57.06	3	0.26	0.24						0.20
K(t)-2,4-DP2	-43.00	3	0.32	0.26						0.19
K(t)-2,4-DB1	-36.67	4		0.25	0.29	0.25		0.20
K(t)-2,4-DB2	-19.84	4		0.26	0.26	0.27		0.24
K(t)-MCPA1	-24.16	4	0.27	0.27	0.31	0.31
K(t)-MCPP1	-36.90	3	0.26	0.27						0.20
K(t)-MCPP2	-36.05	3	0.29	0.28						0.18
K(t)-MCPP3	-1.51	2	0.28	0.26
K(t)-MCPB1	-13.01	3	0.25	0.26				0.24
K(t)-MCPB2	-9.33	4	0.26	0.27	0.27			0.25

Table 1 Hydrogen bond lengths(d) of various low energy structures for phenoxyalkanoic herbicides on Kaolinite

System	E_A(BSSE)/ (kJ·mol^-1)	$n Hb a$	d(H…O)/nm
			C—H…O				O—H…O
			H1^b	H2^b	H3^b	H4^b		H1^b	H2^b	H3^b	H4^b
K(o)-2,4-D1	-35.36	3	0.28						0.18	0.18
K(o)-2,4-D2	-22.58	3						0.21	0.19	0.22
K(o)-2,4-DP1	-4.48	4			0.22	0.24		0.24	0.21
K(o)-2,4-DB1	-66.99	4	0.28						0.20	0.21	0.15
K(o)-2,4-DB2	-58.04	4						0.24	0.20	0.25	0.16
K(o)-MCPA1	-43.83	4	0.27						0.21	0.23	0.17
K(o)-MCPA2	-42.15	4	0.27						0.21	0.22	0.18
K(o)-MCPP1	-60.82	4		0.26				0.20		0.16	0.26
K(o)-MCPP2	-31.60	4						0.20	0.23	0.17	0.19
K(o)-MCPP3	-17.05	3	0.26						0.21	0.20
K(o)-MCPB1	-65.96	4	0.23	0.26	0.26						0.20
K(o)-MCPB2	-7.84	3		0.24	0.25			0.21
K(t)-2,4-D1	-33.62	3	0.27	0.27						0.22
K(t)-2,4-D2	-29.83	3	0.28	0.27						0.21
K(t)-2,4-DP1	-57.06	3	0.26	0.24						0.20
K(t)-2,4-DP2	-43.00	3	0.32	0.26						0.19
K(t)-2,4-DB1	-36.67	4		0.25	0.29	0.25		0.20
K(t)-2,4-DB2	-19.84	4		0.26	0.26	0.27		0.24
K(t)-MCPA1	-24.16	4	0.27	0.27	0.31	0.31
K(t)-MCPP1	-36.90	3	0.26	0.27						0.20
K(t)-MCPP2	-36.05	3	0.29	0.28						0.18
K(t)-MCPP3	-1.51	2	0.28	0.26
K(t)-MCPB1	-13.01	3	0.25	0.26				0.24
K(t)-MCPB2	-9.33	4	0.26	0.27	0.27			0.25

Table 2 Hydrogen bond angles of various low energy structures for phenoxyalkanoic herbicides on Kaolinite

System	∠C—H…O/(°)				∠O—H…O/(°)
System	H1	H2	H3	H4	H1	H2	H3	H4
K(o)-2,4-D1	114.56					159.38	164.53
K(o)-2,4-D2					132.90	154.53	161.25
K(o)-2,4-DP1			167.66	156.01	135.74	148.37
K(o)-2,4-DB1	165.43					169.83	157.51	175.68
K(o)-2,4-DB2					127.76	156.96	143.26	165.94
K(o)-MCPA1	166.05					140.62	138.72	155.06
K(o)-MCPA2	162.80					141.03	141.94	153.70
K(o)-MCPP1		172.21			155.99		166.43	134.62
K(o)-MCPP2					171.53	132.63	152.16	160.23
K(o)-MCPP3	164.14					171.22	153.37
K(o)-MCPB1	137.11	156.58	133.70					174.15
K(o)-MCPB2		142.36	138.34		159.55
K(t)-2,4-D1	164.17	107.93					126.35
K(t)-2,4-D2	129.26	119.49					130.73
K(t)-2,4-DP1	143.53	140.18					164.62
K(t)-2,4-DP2	138.70	138.04					152.88
K(t)-2,4-DB1		170.25	167.89	130.29	147.94
K(t)-2,4-DB2		162.13	158.40	133.63	144.75
K(t)-MCPA1	124.80	123.48	147.50	115.72
K(t)-MCPP1	146.44	154.93					147.49
K(t)-MCPP2	140.14	176.95					156.98
K(t)-MCPP3	169.50	176.32
K(t)-MCPB1	156.56	169.08			150.60
K(t)-MCPB2	136.01	140.13	127.78		148.85

Table 3 Natural bond orbital charges variation(Δq) of the interaction sites before and after the adsorption of pesticides on octahedral surface*

System	Atom	Δq/e	Δq_total/e	System	Atom	Δq/e	Δq_total/e
K(o)-2,4-D1	H14	0.007	-0.011	K(o)-MCPA2	O20	-0.036
	O18	-0.060			O21	-0.048
	H19	0.029			H22	0.025
	C(benzene)	0.013			C(benzene)	0.008
K(o)-2,4-D2	O12	-0.047	0.002	K(o)-MCPP1	H8	0.022	-0.051
	O17	-0.037			O20	-0.023
	H19	0.030			O21	-0.059
	C(benzene)	0.028			H25	0.024
K(o)-2,4-DP1	H11	0.028	-0.008		C(benzene)	0.001
	H14	0.043		K(o)-MCPP2	O12	-0.054	-0.025
	O17	0.015			O20	-0.015
	O18	-0.059			O21	-0.060
	C(benzene)	-0.030			H25	0.036
K(o)-2,4-DB1	H8	-0.012	-0.050		C(benzene)	0.025
	O23	-0.092		K(o)-MCPP3	O12	-0.024	0.018
	H25	0.029			H13	0.012
	C(benzene)	-0.012			O21	-0.052
K(o)-2,4-DB2	O23	-0.069	-0.043		C(benzene)	0.006
	O24	-0.015		K(o)-MCPB1	H8	0.011	-0.012
	H25	0.033			H11	0.022
	C(benzene)	-0.003			H23	0.031
K(o)-MCPA1	H13	0.026	-0.028		O27	-0.023
	O20	-0.035			C(benzene)	-0.006
	O21	-0.048		K(o)-MCPB2	H18	0.039	0.003
	H22	0.026			H24	0.034
	C(benzene)	0.009			O26	-0.039
K(o)-MCPA2	H13	0.019	-0.027		C(benzene)	-0.017

Fig.5 Optimal structures of pesticides on tetrahedral surface

Table 4 Natural bond orbital charges variation of the interaction sites before and after the adsorption of pesticides on tetrahedral surface*

System	Atom	Δq/e	Δq_total/e	System	Atom	Δq/e	Δq_total/e
K(t)-2,4-D1	H11	0.027	-0.017	K(t)-MCPA1	H8	0.014	-0.006
	H14	0.003			H11	0.030
	H19	0.013			H17	0.027
	C(benzene)	-0.002			H18	0.011
K(t)-2,4-D2	H14	-0.002	-0.015		C(benzene)	-0.003
	H15	0.018		K(t)-MCPP1	H8	0.017	-0.022
	H19	0.017			C16	0.003
	C(benzene)	0.004			H17	0.017
K(t)-2,4-DP1	H8	0.021	-0.030		H25	0.020
	H11	0.030			C(benzene)	0.042
	H22	0.022		K(t)-MCPP2	H13	0.017	-0.035
	C(benzene)	0.022			H15	0.008
K(t)-2,4-DP2	H8	0.006	-0.024		H25	0.032
	H11	0.016			C(benzene)	0.007
	H22	0.029		K(t)-MCPP3	H6	0.015	-0.005
	C(benzene)	0.021			H15	0.030
K(t)-2,4-DB1	H11	0.030	-0.035		C(benzene)	0.001
	H15	0.023		K(t)-MCPB1	H18	0.029	-0.008
	H21	0.019			H24	0.008
	H25	0.017			H28	0.011
	C(benzene)	-0.012			C(benzene)	0.041
K(t)- 2,4-DB2	H11	0.022	-0.014	K(t)-MCPB2	H18	0.027	-0.004
	H14	0.030			H20	0.014
	H20	0.009			H24	-0.000
	H25	0.009			H28	0.010
	C(benzene)	0.037			C(benzene)	0.043

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