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The Church’s doctrine of a final purification was already present in the patristic period, but the actual word “Purgatory” (Latin purgatorium) does not appear in the early Fathers’ writings. The first explicit use of the term in an official Church document is found in the papal bull Benedictus Deus issued by Pope Benedict XII in 1336.
In that bull the Pope formally defines the “Purgatory” as a state of purification for the elect, distinguishing it from the punishment of the damned. (1)
Earlier writers (e.g., Ambrose, Augustine, Gregory the Great) spoke of “purifying fire” or “purifying sufferings,” but they did not use the specific term.
Thus, the first known occurrence of the word “Purgatory” in the Church is in Pope Benedict XII’s 1336 decree Benedictus Deus.
References:
III. The Final Purification, or Purgatory
.
.
1031 The Church gives the name Purgatory to this final purification of the elect, which is entirely different from the punishment of the damned. (cf. Council of Florence (1439):DS 1304; Council Of Trent (1563):DS 1820; (1547):1580; see also Benedict XII, Benedictus Deus (1336):DS 1000) The Church formulated her doctrine of faith on Purgatory especially at the Councils of Florence and Trent. The tradition of the Church, by reference to certain texts of Scripture, speaks of a cleansing fire: (cf. 1 Corinthians 3:15; 1 Peter 1:7):
As for certain lesser faults, we must believe
that, before the Final Judgment, there is a purifying
fire. He who is truth says that whoever utters
blasphemy against the Holy Spirit will be pardoned
neither in this age nor in the age to come. From
this sentence we understand that certain offenses
can be forgiven in this age, but certain others
in the age to come.
St. Gregory the Great, Dial. 4,39:PL
77,396; cf. Matthew 12:31-32.