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To cope with regulatory standards, minimizing tailpipe emissions with rapid catalyst light-off during cold-start is critical. This requires catalyst-heating operation with increased exhaust enthalpy, typically by using late post injections for retarded combustion and, therefore, increased exhaust temperature. However, retardability of post injection(s) is constrained by acceptable pollutant emissions such as unburned hydrocarbon (UHC). This study provides further insight into the mechanisms that control the formation of UHC under catalyst-heating operation in a medium-duty diesel engine, and based on the understanding, develops combustion strategies to simultaneously improve exhaust enthalpy and reduce harmful emissions. Experiments were performed with a full boiling-range diesel fuel (cetane number of 45) using an optimized five-injections strategy (2 pilots, 1 main, and 2 posts) as baseline condition.