There are at least two that come to my mind immediately - hydrogen peroxide (H2O2), hydrazine (N2H4) can decompose exothermically with the aid of catalysts. Under normal circumstances such single component exothermic reactions are not found since, if present they would exhaust themselves in accidental ignition processes.
A chemical reaction that begins with only one reactant is called a decomposition reaction. In a decomposition reaction, a single compound breaks down into two or more simpler substances.
A combustion reaction, on the other hand, is a specific type of chemical reaction where a substance reacts rapidly with oxygen gas, producing heat and light. Combustion reactions usually involve organic compounds (containing carbon and hydrogen) and produce carbon dioxide and water as products. Unlike other reactions, combustion reactions involve the combination of a substance with oxygen to produce heat, and they are often associated with flames and burning.
The reaction in which only one reactant gives rise to two or more products is called a Decomposition reaction. Decomposition reaction involves the breakdown of a compound. In contrast to decomposition, combination reactions involve combining two or more compounds to form a single product. Decomposition reactions "take things apart". Just as synthesis reactions can only form one product, decomposition reactions can only start with one reactant. In a combination reaction, a single product is formed and in a decomposition reaction, only one reactant is involved. A chemical reaction having only one reactant is mostly a decomposition reaction. In such a reaction one compound decomposes to form two or more simpler substances. Chemical equilibrium can be attained whether the reaction begins with all reactants and no products, all products and no reactants, or some of both. A reaction that depends on the concentration of only one reactant (a unimolecular reaction). Other reactants can be present, but each will be zero-order. Second-order reaction: A reaction that depends on the concentration(s) of one second-order reactant or two first-order reactants. A composition reaction produces a single substance from multiple reactants. A decomposition reaction produces multiple products from a single reactant. Combustion reactions are the combination of some compound with oxygen to make oxides of the other elements as products (although nitrogen atoms react to make N2). A combustion reaction occurs when oxygen gas (O2) reacts with certain types of compounds. We often call the other compound fuel. A more familiar term for combustion reactions is burning. The most common products of combustion reactions are carbon dioxide and water.