Organic-inorganic hybridization transition-rare earth dissimilar metal substituted germanium tungstate crystal hydrogen storage material and preparation method thereof

Abstract

The invention belongs to the technical field of preparation of novel chemical materials, and particularly relates to an organic-inorganic hybridization transition-rare earth dissimilar metal germanium tungstate crystal hydrogen storage material. The chemical formula of the crystal hydrogen storage material is Na3H7[Cu(en)2]5[Cu (en)2(H2O)]2[(alpha-GeW11O39RE)2(alpha-GeW11O39RE(H2O))(alpha-GeW11O39RE(H2O)2)(WO4)2].13H2O, wherein RE represents Gd<3+> or Y<3+>, and en represents ethylene diamine. The crystal hydrogen storage material is prepared by utilizing the reaction of rare earth ions, transition metal ions, organic ligands and omission Keggin germanium tungstate under a hydrothermal condition. The crystal hydrogen storage material disclosed by the invention has high stability and better absorption property on hydrogen, can perform desorption when temperature increases; and besides, the preparation method disclosed by the invention is simple, easy to operate and lower in cost, and has potential application prospect.

Description

technical field

[0001] The invention belongs to the technical field of preparation of new chemical materials, and specifically relates to an organic-inorganic hybrid transition-rare earth heterometallic substituted germanium tungstate crystalline hydrogen storage material and a preparation method thereof. The material utilizes rare earth ions, transition metal ions, organic The ligand is prepared by reacting with vacant Keggin germanium tungstate under hydrothermal conditions. Background technique

[0002] Polyoxometalates are a class of compounds with remarkable structural characteristics formed by the connection of early transition metal ions through oxygen atoms. In terms of composition, the framework elements of polyoxometalates are usually some high-valence pre-transition metal ions, such as Mo(VI), W(VI), V(V), Nb(V) and Ta(V). Structurally speaking, the basic unit of polyoxometalates is mainly MO 6 Octahedral (M generally represents metal ion) and XO 4 Tetrahedra (...

Examples

Embodiment 1

[0035] Example 1: Na 3 h 7 [Cu(en) 2 ] 5 [Cu(en) 2 (H 2 O)] 2 [(α-GeW 11 o 39 Gd) 2 (α-GeW 11 o 39 Gd(H 2 O))

[0036] (α-GeW 11 o 39 Gd (H 2 O) 2 ) (WO 4 ) 2 ]·13H 2 Preparation of O crystalline hydrogen storage materials:

[0037] 1) Synthesize the required triple-deficient germanium tungstate precursor K according to the literature method 8 Na 2 [A-α-GeW 9 o 34 ]·25H 2 O, see L. H. Bi, U. Kortz, S. Nellutla, A. C. Stowe, J. van Tol, N. S. Dalal, B. Keita, L. Nadjo, Inorg. Chem. 2005, 44, 896);

[0038] 2) 3.62 g (0.01 mol) rare earth oxide Gd 2 o 3 Dissolve in 6.70 mL, 12 mol L under heating –1 Concentrated hydrochloric acid (0.08mol), and then heated and evaporated to dryness at 80°C (about 40 min) to obtain anhydrous GdCl 3 , cooled and sealed for storage;

[0039] 3) Under stirring conditions, 330mg (0.107mmol) K 8 Na 2 [A-α-GeW 9 o 34 ]·25H 2 O, 68 mg (0.399 mmol) CuCl 2 2H 2 O, 68 mg (0.258 mmol) GdCl 3 and 0.1mL (1.480mmol) of e...

Embodiment 2

[0040] Example 2: Na 3 h 7 [Cu(en) 2 ] 5 [Cu(en) 2 (H 2 O)] 2 [(α-GeW 11 o 39 Gd) 2 (α-GeW 11 o 39 Gd(H 2 O))

[0041] (α-GeW 11 o 39 Gd (H 2 O) 2 ) (WO 4 ) 2 ]·13H 2 Preparation of O crystalline hydrogen storage materials:

[0042] 1) Synthesize the required triple-deficient germanium tungstate precursor K according to the literature method 8 Na 2 [A-α-GeW 9 o 34 ]·25H 2 O, see L. H. Bi, U. Kortz, S. Nellutla, A. C. Stowe, J. van Tol, N. S. Dalal, B. Keita, L. Nadjo, Inorg. Chem. 2005, 44, 896);

[0043] 2) 3.62 g (0.01 mol) rare earth oxide Gd 2 o 3 Dissolve in 6.70 mL, 12 mol L under heating –1 Concentrated hydrochloric acid (0.08mol), then heated and evaporated to dryness at 90°C to obtain anhydrous GdCl 3 , cooled and sealed for storage;

[0044] 3) Under stirring conditions, 330mg (0.107mmol) K 8 Na 2 [A-α-GeW 9 o 34 ]·25H 2 O, 68 mg (0.399 mmol) CuCl 2 2H 2 O, 68 mg (0.258 mmol) GdCl 3 and 0.05mL (0.740mmol) of ethylenediamine wer...

Embodiment 3

[0045] Example 3: Na 3 h 7 [Cu(en) 2 ] 5 [Cu(en) 2 (H2 O)] 2 [(α-GeW 11 o 39 Y) 2 (α-GeW 11 o 39 Y(H 2 O))(α-GeW 11 o 39 Y (H 2 O) 2 ) (WO 4 ) 2 ]·13H 2 Preparation of O crystalline hydrogen storage materials:

[0046] 1) Synthesize the required triple-deficient germanium tungstate precursor K according to the literature method 8 Na 2 [A-α-GeW 9 o 34 ]·25H 2 O, see L. H. Bi, U. Kortz, S. Nellutla, A. C. Stowe, J. van Tol, N. S. Dalal, B. Keita, L. Nadjo, Inorg. Chem. 2005, 44, 896);

[0047] 2) 2.26 g (0.01 mol) rare earth oxide Y 2 o 3 Dissolve in 6.70 mL, 12 mol L under heating –1 Concentrated hydrochloric acid (0.08mol), and then heated and evaporated to dryness at 80°C (about 30min) to obtain anhydrous YCl 3 , cooled and sealed for storage;

[0048] 3) Under stirring conditions, 431mg (0.140mmol) K 8 Na 2 [A-α-GeW 9 o 34 ]·25H 2 O, 63 mg (0.370 mmol) CuCl 2 2H 2 O, 98mg (0.502mmol) YCl 3 and 0.1mL (1.480mmol) of ethylenediamine were ad...

technical field

[0001] The invention belongs to the technical field of preparation of new chemical materials, and specifically relates to an organic-inorganic hybrid transition-rare earth heterometallic substituted germanium tungstate crystalline hydrogen storage material and a preparation method thereof. The material utilizes rare earth ions, transition metal ions, organic The ligand is prepared by reacting with vacant Keggin germanium tungstate under hydrothermal conditions. Background technique

[0002] Polyoxometalates are a class of compounds with remarkable structural characteristics formed by the connection of early transition metal ions through oxygen atoms. In terms of composition, the framework elements of polyoxometalates are usually some high-valence pre-transition metal ions, such as Mo(VI), W(VI), V(V), Nb(V) and Ta(V). Structurally speaking, the basic unit of polyoxometalates is mainly MO 6 Octahedral (M generally represents metal ion) and XO 4 Tetrahedra (...

Examples

Embodiment 1

[0035] Example 1: Na 3 h 7 [Cu(en) 2 ] 5 [Cu(en) 2 (H 2 O)] 2 [(α-GeW 11 o 39 Gd) 2 (α-GeW 11 o 39 Gd(H 2 O))

[0036] (α-GeW 11 o 39 Gd (H 2 O) 2 ) (WO 4 ) 2 ]·13H 2 Preparation of O crystalline hydrogen storage materials:

[0037] 1) Synthesize the required triple-deficient germanium tungstate precursor K according to the literature method 8 Na 2 [A-α-GeW 9 o 34 ]·25H 2 O, see L. H. Bi, U. Kortz, S. Nellutla, A. C. Stowe, J. van Tol, N. S. Dalal, B. Keita, L. Nadjo, Inorg. Chem. 2005, 44, 896);

[0038] 2) 3.62 g (0.01 mol) rare earth oxide Gd 2 o 3 Dissolve in 6.70 mL, 12 mol L under heating –1 Concentrated hydrochloric acid (0.08mol), and then heated and evaporated to dryness at 80°C (about 40 min) to obtain anhydrous GdCl 3 , cooled and sealed for storage;

[0039] 3) Under stirring conditions, 330mg (0.107mmol) K 8 Na 2 [A-α-GeW 9 o 34 ]·25H 2 O, 68 mg (0.399 mmol) CuCl 2 2H 2 O, 68 mg (0.258 mmol) GdCl 3 and 0.1mL (1.480mmol) of e...

Embodiment 2

[0040] Example 2: Na 3 h 7 [Cu(en) 2 ] 5 [Cu(en) 2 (H 2 O)] 2 [(α-GeW 11 o 39 Gd) 2 (α-GeW 11 o 39 Gd(H 2 O))

[0041] (α-GeW 11 o 39 Gd (H 2 O) 2 ) (WO 4 ) 2 ]·13H 2 Preparation of O crystalline hydrogen storage materials:

[0042] 1) Synthesize the required triple-deficient germanium tungstate precursor K according to the literature method 8 Na 2 [A-α-GeW 9 o 34 ]·25H 2 O, see L. H. Bi, U. Kortz, S. Nellutla, A. C. Stowe, J. van Tol, N. S. Dalal, B. Keita, L. Nadjo, Inorg. Chem. 2005, 44, 896);

[0043] 2) 3.62 g (0.01 mol) rare earth oxide Gd 2 o 3 Dissolve in 6.70 mL, 12 mol L under heating –1 Concentrated hydrochloric acid (0.08mol), then heated and evaporated to dryness at 90°C to obtain anhydrous GdCl 3 , cooled and sealed for storage;

[0044] 3) Under stirring conditions, 330mg (0.107mmol) K 8 Na 2 [A-α-GeW 9 o 34 ]·25H 2 O, 68 mg (0.399 mmol) CuCl 2 2H 2 O, 68 mg (0.258 mmol) GdCl 3 and 0.05mL (0.740mmol) of ethylenediamine wer...

Embodiment 3

[0045] Example 3: Na 3 h 7 [Cu(en) 2 ] 5 [Cu(en) 2 (H2 O)] 2 [(α-GeW 11 o 39 Y) 2 (α-GeW 11 o 39 Y(H 2 O))(α-GeW 11 o 39 Y (H 2 O) 2 ) (WO 4 ) 2 ]·13H 2 Preparation of O crystalline hydrogen storage materials:

[0046] 1) Synthesize the required triple-deficient germanium tungstate precursor K according to the literature method 8 Na 2 [A-α-GeW 9 o 34 ]·25H 2 O, see L. H. Bi, U. Kortz, S. Nellutla, A. C. Stowe, J. van Tol, N. S. Dalal, B. Keita, L. Nadjo, Inorg. Chem. 2005, 44, 896);

[0047] 2) 2.26 g (0.01 mol) rare earth oxide Y 2 o 3 Dissolve in 6.70 mL, 12 mol L under heating –1 Concentrated hydrochloric acid (0.08mol), and then heated and evaporated to dryness at 80°C (about 30min) to obtain anhydrous YCl 3 , cooled and sealed for storage;

[0048] 3) Under stirring conditions, 431mg (0.140mmol) K 8 Na 2 [A-α-GeW 9 o 34 ]·25H 2 O, 63 mg (0.370 mmol) CuCl 2 2H 2 O, 98mg (0.502mmol) YCl 3 and 0.1mL (1.480mmol) of ethylenediamine were ad...

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