Electron acceptor compositions on polymer templates

• US 5,906,892 A
• Filed: 08/21/1995
• Issued: 05/25/1999
• Est. Priority Date: 08/09/1993
• Status: Expired due to Term

• Current Assignee: Princeton University
• Original Assignee: The Trustees of Princeton University (Princeton University)
• Inventors: Thompson, Mark E., Tang, Xiaozhang
• Primary Examiner(s): CODD, BERNARD P
• Application Number:
  US08/517,095
• Time in Patent Office: 1,373 Days
• Field of Search: 428/411.1, 428/457, 428/689, 525/361, 525/362, 525/364, 525/340, 544/225, 544/226, 546/213, 427/380, 427/383.1, 427/383.3, 427/383.5, 427/383.7, 427/384, 427/388.1, 427/388.4, 427/407.2, 427/409, 427/412.1, 427/419.8
• US Class Current: 428/411.1
• CPC Class Codes: B01J 21/08 Silica
• CPC Class Codes: B01J 2231/62 Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
• CPC Class Codes: B01J 2231/645 of C=C or C-C triple bonds
• CPC Class Codes: B01J 2231/70 Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
• CPC Class Codes: B01J 23/40 of the platinum group metals
• CPC Class Codes: B01J 23/42 Platinum
• CPC Class Codes: B01J 2531/48 Zirconium
• CPC Class Codes: B01J 2531/824 Palladium
• CPC Class Codes: B01J 2531/828 Platinum
• CPC Class Codes: B01J 31/1658 immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins
• CPC Class Codes: B01J 31/1691 Coordination polymers, e.g. metal-organic frameworks [MOF] preparation of metal complexes containing carboxylic acid moieties C07C51/418; MOF's per se C07F
• CPC Class Codes: B01J 31/185 Phosphites ((RO)3P) , their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
• CPC Class Codes: B01J 31/189 containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
• CPC Class Codes: B01J 35/23 in a colloidal state
• CPC Class Codes: B01J 35/39 Photocatalytic properties
• CPC Class Codes: B01J 35/393 Metal or metal oxide crystallite size
• CPC Class Codes: B01J 37/0209 involving a reaction between the support and a fluid
• CPC Class Codes: B01J 37/30 Ion-exchange
• CPC Class Codes: C01B 15/029 Preparation from hydrogen and oxygen
• CPC Class Codes: C01B 3/042 Decomposition of water
• CPC Class Codes: C07F 9/58 : Pyridine rings
• CPC Class Codes: C08F 230/02 : containing phosphorus
• CPC Class Codes: C08F 230/04 : containing a metal
• CPC Class Codes: C08F 26/06 : by a heterocyclic ring containing nitrogen
• CPC Class Codes: C08F 30/02 : containing phosphorus
• CPC Class Codes: C08F 30/04 : containing a metal
• CPC Class Codes: C08F 8/02 : Alkylation
• CPC Class Codes: C08F 8/40 : Introducing phosphorus atoms or phosphorus-containing groups
• CPC Class Codes: C08F 8/44 : Preparation of metal salts or ammonium salts
• CPC Class Codes: Y02E 60/36 : Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
• CPC Class Codes: Y02P 20/133 : Renewable energy sources, e.g. sunlight
• CPC Class Codes: Y10T 292/702 : Pivoted or swinging
• CPC Class Codes: Y10T 428/31504 : Composite [nonstructural laminate]
• CPC Class Codes: Y10T 428/31678 : Of metal

Abstract

Stable electron acceptor compositions are composed of a plurality of pillared metal complexes disposed on a supporting substrate. At least one Group VIII metal at zero valence is entrapped within this matrix. The complexes comprise from one to about 100 units of the formula:

--(Y.sup.1 O.sub.3 --Z--Y.sup.2 O.sub.3)Me.sup.Y --

Y¹ and Y² being phosphorus or arsenic; Z being a divalent group which reversibly forms a stable reduced form and contains two conjugated cationic centers having a negative E.sup.∘_red value; and Me^Y being a divalent, trivalent, or tetravalent metal of Group IIIA, IIIB, IVA, or IVB having an atomic number of at least 21 or a lanthanide with bonded anions. The units are bound to the substrate through an organic polymer having side chains derivatized with phosphonate or arsonate groups. Counter anions balance the charge of Z. The compositions can be used in the decomposition of water to yield hydrogen gas, the sensing of oxygen, and as catalysts.

Claims

1. An article comprising a supporting substrate having on its surface a film comprising:

(I) a plurality of a complex of the formula;

space="preserve" listing-type="equation">--L-- Y.sup.1 O.sub.3 --Z--Y.sup.2 O.sub.3)Me.sup.Y !.sub.k.kp(X.sup.q-)

wherein

L is a linking means;

each of Y¹ and Y², independently of the other, is phosphorus or arsenic;

Z is a divalent group which reversibly forms a stable reduced form and contains two conjugated cationic centers which together have a negative E.sup.∘

_red value;

X is an anion;

Me^Y is Me¹_n W_m, where

Me¹ is a divalent, trivalent, or tetravalent metal of Group IIIA, IIIB, IVA, or IVB having an atomic number of at least 21 or a lanthanide;

W is an anion;

n is 1, 2, or 3;

m is 0, 1, 2, 3, or 4;

k has a value of from 1 to about 100;

p has a value of 0, 1, 2, or 3; and

q is the charge on X,

wherein each of Y¹, Y², Z, and Me¹ may be different for each successive k;

wherein each of said complexes is bound to said substrate through the linking means, L, which is an organic polymer having side chains with phosphonate or arsonate groups.

2. The article of claim 1, wherein the film further comprises colloidal particles of at least one Group VIII metal at zero valence entrapped within said complexes by the Me¹ atoms.

3. The article of claim 1 wherein the substrate is an organic polymer, and wherein said linking means are side chains on said organic polymer, said side chains having phosphonate or arsonate groups.

4. An article comprising a supporting substrate having on its surface a film, said film comprising:

(I) two or more adjacent metal layers;

(ii) organic pillars covalently joined to two of said adjacent metal layers;

(iii) linking means binding said substrate to the metal layer closest to the substrate;

ps wherein;

each metal layer, independently of the other, comprises;

a) atoms of a trivalent or tetravalent metal of Group IIIA, IIIB, IVA, IVB having an atomic number of at least 21 or atoms of a lanthanide, forming a cohesive layer; and

,

b) anions bound to the metal atoms such that the metal ions have an effective valence of from ⁺ 1 to ⁺ 6;

said organic pillars are illustrated by the formula;

space="preserve" listing-type="equation">--(Y.sup.1 O.sub.3 --Z--Y.sup.2 O.sub.3)--.p(X.sup.-q)

each of Y¹ and Y², independently of the other, is phosphorous or arsenic;

Z is an electron accepting divalent group containing two conjugated cationic centers which together have a negative E.sup.∘

_red value, wherein Z is capable of alternating between a stable reduced form and a stable oxidized form;

X is an anion;

p has a value of 0, 1, 2 or 3; and

,

q is the charge on X;

and,

the linking means is an organic polymer having side chains with phosphonate or arsonate groups.

5. The article of claim 4, wherein the film further comprises colloidal particles of at least one Group VIII metal at zero valence entrapped within said complexes by the metal atoms.

10. The article of claims 4, 5, 6, 7, or 8, further comprising organic ligands, said ligands being disposed between said metal layers and between said pillars, each of said ligands being independently, one from the other, covalently joined to one of said adjacent metal layers;

wherein said ligands are illustrated by the formula;

space="preserve" listing-type="equation">--Y.sup.3 O.sub.3 --R.sup.3

Y³ is phosphorous or arsenic; and

,

R³ is a non-reducible capping group.

6. A article comprising a supporting substrate having on its surface a film, said film comprising:

(I) two or more adjacent metal layers;

(ii) organic pillars covalently joined to two of said adjacent metal layers;

wherein;

each metal layer, independently of the other, comprises

a) atoms of a trivalent or tetravalent metal of Group IIIA, IIIB, IVA, IVB having an atomic number of at least 21 or atoms of a lanthanide; and

,

b) anions bound to the metal atoms such that the metal ions have an effective valence of from ⁺ 1 to ⁺ 6;

forming a cohesive layer;

said organic pillars are illustrated by the formula;

space="preserve" listing-type="equation">--(Y.sup.1 O.sub.3 --Z--Y.sup.2 O.sub.3)--.p(X.sup.-q)

each of Y¹ and Y², independently of the other, is phosphorous or arsenic;

Z is an electron accepting divalent group containing two conjugated cationic centers which together have a negative E.sup.∘

_red value, wherein Z is capable of alternating between a stable reduced form and a stable oxidized form;

X is an anion;

p has a value of 0, 1, 2 or 3; and

,

q is the charge on X; and

,

said substrate is an organic polymer having side chains with phosphonate or arsonate groups.

7. The article of claim 6, further comprising colloidal particles of a Group VIII metal, said particles being trapped within the hydrophobic environment between polymer backbones.

8. The article of claim 6 wherein the film further comprises colloidal particles of at least one Group VIII metal at zero valence entrapped within interstices formed between the pillars and metal layers.

9. The method for producing the articles of claim 6 comprising the steps of:

A) dissolving an organic polymer having side chains derivatized with phosphonate or arsonate groups in a solution of colloidal particles of a Group VIII metal;

B) adding a solution comprising ions of a tirvalent or tetravalent metal of Group IIIA, IIIB, IVA, or IVB having an atomic number of at least 21 or a lanthanide;

C) crosslinking the phosphonate or arsonate groups with the metal ions;

D) dialyzing the mixture against distilled water to remove free ions;

E) adding a bisphosphonic or bisarsonic acid;

F) dialyzing the mixture against distilled water to remove free ions; and

,

G) repeatedly performing steps B, C, D, E, and F.

11. An article comprising a supporting substrate having on its surface a film, said film comprising a first layer and one or more successive layers, each layer independently of the other comprising:

(I) a plurality of the complex illustrated by the formula

space="preserve" listing-type="equation">-- (Y.sup.1 O.sub.3 --Z--Y.sup.2 O.sub.3)Me.sup.Y !.p(X.sup.q-)

wherein

each of Y¹ and Y², independently of the other, is phosphorus or arsenic;

Z is a divalent group which reversibly forms a stable reduced form and contains two conjugated cationic centers which together have a negative E.sup.∘

_red value;

X is an anion;

Me^Y is Me¹_n W_m, where

Me¹ is a divalent, trivalent, or tetravalent metal of Group IIIA, IIIB, IVA, or IVB having an atomic number of at least 21 or a lanthanide;

W is an anion;

n is 1, 2, or 3;

m is 0, 1, 2, 3, or 4 said plurality of Me^Y forming a cohesive layer;

p has a value of 0, 1, 2, or 3; and

q is the charge on X,

wherein the (Y¹ O₃ --Z--Y² O₃) parts of said complexes are perpendicular to the substrate and said Me^Y cohesive layers are parallel to substrate; and

,

wherein the first layer is bound to said substrate through a linking means having the formula;

space="preserve" listing-type="equation">--L--Me.sup.Z

wherein L is an organic polymer having side chains with phosphonate or arsonate groups; and

Me^Z is Me³_s W'"'"'_t, where Me³ is a trivalent or tetravalent metal of Group IIIA, IIIB, IVA, or IVB having an atomic number of at least 21 or a lanthanide, crosslinking the phosphonate or arsonate groups of the polymer forming a cohesive layer;

W'"'"' is an anion;

s is 1, 2, or 3; and

,

t is 0, 1, 2, 3, or 4;

where the plurality of --(Y¹ O₃ --Z--Y² O₃) of the first layer are covalently bonded to the Me^Z cohesive layer; and

,

where the plurality of --(Y¹ O₃ --Z--Y² O₃) of each successive layer are covalently bonded to the Me^Y layer of the preceding layer.