The DEF is injected into the exhaust system and reacts with the NOX to break it into nitrogen gas and water vapor. It works entirely "downstream" of the engine.
All Tier IV engines have NOX sensors in the exhaust system to make sure the system is working per the EPA regulations. If a person tried to use just water or even diluted DEF in place of the full strength DEF the sensors would detect the increased NOX and would derate the engine. In addition, the use of a DEF quality sensor in the tank is also being pushed by the EPA which would trip the derate system even before the exhaust stream sensors detected anything.
I've also heard of guys mistakenly putting diesel into the DEF tank. This is very bad because it will quickly damage some very expensive components in the exhaust system.
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