Membranes of the present disclosure possess very thin barrier layers, with high selectivity, high throughput, low fouling, and are long lasting. The membranes include graphene and/or graphene oxide barrier layers on a nanofibrous supporting scaffold. Methods for forming these membranes, as well as uses thereof, are also provided. In embodiments, an article of the present disclosure includes a nanofibrous scaffold; at least a first layer of nanoporous graphene, nanoporous graphene oxide, or combinations thereof on at least a portion of a surface of the nanofibrous scaffold; an additive such as crosslinking agents and/or particles on an outer surface of the at least first layer of nanoporous graphene, nanoporous graphene oxide, or combinations thereof.