There are quite a number of other reducing agents that can be applied in the synthesis of gold or silver nanoclusters, such as chitosan, folic acid, ascobic acid and even materials of biological origin, some plant extracts, bacteria and fungi extracts. These can also reduce metallic salts to form their nanoparticles.
Yes you can use Na-citrate, PEG, PEI (poly ethylene imine) also.
Again you may synthesize using green chemistry method by plant leaf extract.
Please see these papers:
1. Green synthesis and characterization of monodispersed gold nanoparticles: Toxicity study, delivery of doxorubicin and its biodistribution in mouse model
2. Green chemistry approach for the synthesis of gold nanoconjugates that induces the inhibition of cancer cells proliferation through induction of oxidative stress and their in vivo toxicity study
3. Potential therapeutic and diagnostic applications of one-step in situ biosynthesized gold nanoconjugates (2-in-1 system) in cancer treatment
If you are going to synthesizing cluster (sub 3 nm), I think the best option is NaBH4. but for bigger particle you can use any other reducing agent that other member of panel suggested.
There are a wealth of possibilities. I'd avoid borohydride reduction as all produced metals then get contaminated with B. I used 5% hydrazine hydrate (as only N2 and water are the products) in my PhD, but you can use H2 and these days some people are favoring (hard to characterize) plant extracts. See, for example (registration needed):