Described herein is a simple and versatile synthetic strategy for the preparation of metal-organic frameworks comprising a carbon matrix doped with nitrogen atoms, wherein transition metal ions are bonded to the carbon matrix via the nitrogen atoms. This strategy is applicable for the synthesis of single metal catalysts or multi metal catalysts rich with atomically dispersed metal active sites. The metal-organic frameworks provided herein have numerous application when used in fuel cells.

The present invention provides a catalyst which has oxygen reduction catalytic ability surpassing that of a platinum-carrying carbon material. This catalyst comprises a carbon material and a metal complex represented by formula (1).

##STR00001##

In formula (1), X.sup.1 to X.sup.8 each independently represent a hydrogen atom or a halogen atom, D.sup.1 to D.sup.4 each represent a nitrogen atom or a carbon atom wherein the carbon atom has bound thereto a hydrogen atom or a halogen atom, and M represents a metallic atom.

A nanofibrous catalyst for in the electrolyzer and methods of making the catalyst. The catalysts are composed of highly porous transition metal carbonitrides, metal oxides or perovskites derived from the metal-organic frameworks and integrated into a 3D porous nano-network electrode architecture. The catalysts are low-cost, highly active toward OER, with excellent conductivity yet resistant to the oxidation under high potential operable under both acidic and alkaline environments.

The invention relates to compounds of formula (I)

##STR00001##

where
R.sup.1, R.sup.2, R.sup.3, R.sup.4 are each independently selected from —(C.sub.1-C.sub.12)-alkyl, —(C.sub.3-C.sub.12)-cycloalkyl, —(C.sub.3-C.sub.12)-heterocycloalkyl, —(C.sub.6-C.sub.20)-aryl, —(C.sub.3-C.sub.20)-heteroaryl;
at least one of the R.sup.1, R.sup.2, R.sup.3, R.sup.4 radicals is a —(C.sub.3-C.sub.20)-heteroaryl radical;
and
R.sup.1, R.sup.2, R.sup.3, R.sup.4, if they are —(C.sub.1-C.sub.12)-alkyl, —(C.sub.3-C.sub.12)-cycloalkyl, —(C.sub.3-C.sub.12)-heterocycloalkyl, —(C.sub.6-C.sub.20)-aryl or —(C.sub.3-C.sub.20)-heteroaryl,
may each independently be substituted by one or more substituents selected from —(C.sub.1-C.sub.12)-alkyl, —(C.sub.3-C.sub.12)-cycloalkyl, —(C.sub.3-C.sub.12)-heterocycloalkyl, —O—(C.sub.1-C.sub.12)-alkyl, —O—(C.sub.1-C.sub.12)-alkyl-(C.sub.6-C.sub.20)-aryl, —O—(C.sub.3-C.sub.12)-cycloalkyl, —S—(C.sub.1-C.sub.12)-alkyl, —S—(C.sub.3-C.sub.12)-cycloalkyl, —COO—(C.sub.1-C.sub.12)-alkyl, —COO—(C.sub.3-C.sub.12)-cycloalkyl, —CONH—(C.sub.1-C.sub.12)-alkyl, —CONH—(C.sub.3-C.sub.12)-cycloalkyl, —CO—(C.sub.1-C.sub.12)-alkyl, —CO—(C.sub.3-C.sub.12)-cycloalkyl, —N—[(C.sub.1-C.sub.12)-alkyl].sub.2, —(C.sub.6-C.sub.20)-aryl, —(C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl, —(C.sub.6-C.sub.20)-aryl-O—(C.sub.1-C.sub.12)-alkyl, —(C.sub.3-C.sub.20)-heteroaryl, —(C.sub.3-C.sub.20)-heteroaryl-(C.sub.1-C.sub.12)-alkyl, —(C.sub.3-C.sub.20)-heteroaryl-O—(C.sub.1-C.sub.12)-alkyl, —COOH, —OH, —SO.sub.3H, —NH.sub.2, halogen;
and to the use thereof as ligands in alkoxycarbonylation.

The present disclosure discloses an immobilized metalloporphyrin catalyst and its utilization in maleic acid preparation, belonging to the technical field of metalloporphyrin catalytic application. The immobilized metalloporphyrin catalyst is used for catalyzing furfural to prepare maleic acid and is good in catalytic effect, mild in reaction conditions and capable of greatly reducing the energy consumption required in the prior art. The catalyst disclosed by the present disclosure can provide a good microenvironment for a reaction, so that the yield and selectivity of maleic acid are increased; and according to a method disclosed by the present disclosure, the conversion ratio of furfural is 20.4%-95.6%, the yield of maleic acid is 10%-56.1%, and the selectivity is 43.6%-76.1%. Meanwhile, the catalyst is easy to separate and environmentally friendly and may be recycled for many times.

A nanocage-confined catalyst has the formula: NC-m[M(Salen1)X]-n[M′(Salen2)]. NC is a material having a nanocage structure, and M(Salen1)X and M′ (Salen2) are active centers, respectively; each occurrence of M is independently selected from the group consisting of Co ion, Fe ion, Ga ion, Al ion, Cr ion, and a mixture thereof. Each occurrence of M′ is independently selected from Cu ion, Ni ion and a mixture thereof, m is 0 to 100; n is 0 to 100, with the proviso that at least one of m and n is not 0; each occurrence of Salen1 and Salen2 is independently a derivative of Shiff bases; X is an axial anion selected from the group consisting of substituted or unsubstituted acetate, substituted or unsubstituted benzene sulfonate, substituted or unsubstituted benzoate, F—, Cl—, Br—, I—, SbF6-, PF6-, BF4-, and a mixture thereof.

Disclosed are N-heterocyclic carbene (NHC) and 4-pyridinol-derived pincer ligands and metal complexes containing these ligands. These compounds can be used to photocatalyticaly reduce CO.sub.2 to CO.

An oxo-nitrogenated iron complex having general formula (I) or (II) wherein: R.sub.1 and R.sub.2 identical or different, represent a hydrogen atom; or are selected from linear or branched, optionally halogenated C.sub.1-C.sub.20, preferably C.sub.1-C.sub.15, alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; R.sub.3, identical or different, represent a hydrogen atom; or are selected from linear or branched, optionally halogenated C.sub.1-C.sub.20, preferably C.sub.1-C.sub.15, alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; X.sub.1 and X.sub.2, identical or different, represent a halogen atom such as, for example, chlorine, bromine, iodine; or are selected from linear or branched C.sub.1-C.sub.20, preferably C.sub.1-C.sub.15, alkyl groups, —OCOR.sub.4 groups or —OR.sub.4 groups wherein R.sub.4 is selected from linear or branched C.sub.1-C.sub.20, preferably C.sub.1-C.sub.15, alkyl groups. Said oxo-nitrogenated iron complex having general formula (I) or (II) can be advantageously used in a catalytic system for the (co)polymerization of conjugated dienes.

Disclosed is a method for preparing a benzyl amine compound, i.e., synthesizing a benzyl amine compound by means of an oxidation reaction between a methylbenzene/ethylbenzene compound and arylamine by using an ionic iron (III) complex containing 1,3-di-tert-butylimidazolium cation and having a molecular formula of [(RNCHCHNR)CH][FeBr.sub.4] (R being tert-butyl) and di-t-butyl peroxide as an oxidant. The present invention is not only applicable to a methylbenzene compound containing a benzylic primary carbon-hydrogen bond but also applicable to an ethylbenzene compound containing a benzylic secondary carbon-hydrogen bond, and therefore is widely applicable. This is the first case where the preparation of a benzyl amine compound by means of an oxidation reaction between a methylbenzene/ethylbenzene compound and arylamine is implemented by an iron catalyst.

Disclosed is an application of an ionic iron (III) complex as a catalyst in preparation of a benzylamine compound, that is, an ionic iron (III) complex having a molecular formula of [(RNCHCHNR)CH][FeBr.sub.4] (R is tert-butyl) and containing 1,3-di-tert-butyl imidazolium cation is used as a catalyst, di-tert-butyl peroxide is used as an oxidizing agent, and a benzylamine compound is synthesized by oxidation reaction of a toluene/ethylbenzene compound with an aromatic amine. The present invention has a wide application range, and is applicable not only to a toluene compound containing a benzylic primary carbon-hydrogen bond but also to an ethylbenzene compound containing a benzyl secondary carbon-hydrogen bond. This is the first example of the preparation of a benzylamine compound by oxidation reaction of a toluene/ethylbenzene compound and an aromatic amine by an iron-based catalyst.