What is the ruling on performing voluntary prayers during official working hours?

All perfect praise be to Allah, The Lord of The Worlds, and may His Peace and Blessings be upon our Prophet Muhammad and upon all of his family and companions

There is no harm if  there was break time during official working hours, but if not then it is impermissible. And Allah Knows Best.

I took a car from the Orphans' Fund Development Institution; is there usury (Riba) involved in this transaction?

If the Sharia's conditions were met, then there is no harm in this. And Allah The Exalted Knows Best.

Is it permissible for a woman who has become pure before the end of forty days of confinement to perform different acts of worship? and is it lawful for her husband to have sex with her?

Once postpartum bleeding ceases and she is certain that it won`t happen again, she becomes pure, and so she should perform Ghusl (ritual bath), pray, and fast. She can also have sex with her husband even before the end of (40) days because the minimum of postpartum bleeding is a moment, and the maximum is (60) days. However, the postpartum bleeding for the majority of women is (40) days, but this does not apply to rest of them.

Is wearing a cap permissible for boys, or girls?

All Perfect Praise is due to Allah, The Lord of The Worlds.

In principle, anything is permissible sol long as there is no Sharia evidence prohibiting it, thus wearing the cap by boys is permissible as long as it isn`t done in imitation of the disbelievers. Moreover, a Muslim woman should avoid all that which attracts the attention of men because whatever leads to the forbidden is forbidden. And Allah Knows Best.