The IEEE 802.15.4a specification targets the low-rate (LR) Impulse-radio (IR) ultra-wideband (UWB) system which is now widely applied in the WPANs considering rather short distance communications with low complexity and power consumption. The physical (PHY) layer uses concatenated coding with mixed binary phase-shift keying and binary pulse-position modulation (BPSK-BPPM), and direct sequence spreading with time hopping in order that both coherent and non-coherent receiver architectures are supported. In this paper, the performances of multiple access schemes compliant with IEEE 802.15.4a specification are investigated with energy detection receiver, which allow avoiding the complex channel estimation needed by a coherent receiver. However, the performance of energy detection receiver is severely degraded by multi-user interference (MUI), which largely diminishes one of the most fascinating advantages of UWB, namely robustness to MUI as well as the possibility to allow parallel transmissions. So as to improve the performance of multiple access schemes, we propose to apply the novel TH sequences as well as to increase the number of TH positions. The simulation results show that our novel multiple access schemes significantly improve the performance against MUI.